Methods for enhancing the mesoporosity of zeolite-containing materials

ABSTRACT

Methods for enhancing the mesoporosity of a zeolite-containing material. Such methods may comprise contacting a composite shaped article containing at least one zeolite and at least one non-zeolitic material with at least one pH controlling agent and at least one surfactant. Such methods may be performed under conditions sufficient to increase the pore volume of at least one 10 angstrom subset of mesoporosity.

RELATED APPLICATIONS

This application is a continuation of U.S. patent application Ser. No.12/907,643, filed Oct. 19, 2010, which claims priority to U.S.Provisional Patent Application Ser. No. 61/253,281, filed Oct. 20, 2009,the entire disclosures of which are incorporated herein by reference.

BACKGROUND

1. Field of the Invention

Various embodiments of the present invention relate generally toenhancing the mesoporosity of a zeolite-containing material. Moreparticularly, various embodiments relate to methods for riving azeolite-containing catalyst.

2. Description of the Related Art

Zeolites and related crystalline molecular sieves are widely used due totheir regular microporous structure, strong acidity, and ion-exchangecapability. However, their applications are limited by their small poreopenings, which are typically narrower than 1 nm. The discovery ofMCM-41, with tuneable mesopores of 2 to 10 nm, overcomes some of thelimitations associated with zeolites. However, unlike zeolites,MCM-41-type materials are not crystalline, and do not possess strongacidity, high hydrothermal stability, and high ion-exchange capability.

Over the past 10 years, a great deal of effort has been devoted tounderstanding and improving the structural characteristics of MCM-41. Itwas found that the properties of Al-MCM-41 could be improved through (1)surface silylation, (2) Al grafting on the pore walls to increaseacidity, (3) salt addition during synthesis to facilitate thecondensation of aluminosilicate groups, (4) use of organics typicallyemployed in zeolite synthesis to transform partially the MCM-41 wall tozeolite-like structures, (5) preparation of zeolite/MCM-41 composites,(6) substitution of cationic surfactants by tri-block copolymers andGemini amine surfactants to thicken the walls, and (7) assembly ofzeolite nanocrystals into an ordered mesoporous structure. In the latterapproach, the first steam-stable hexagonal aluminosilicate (named MSU-S)was prepared using zeolite Y nanoclusters as building blocks. Pentasilzeolite nanoclusters were also used to produce MSU-S_((MFI)) andMSU-S_((BEA)).

FIG. 1A is a schematic illustration of a prior art amorphous mesoporousmaterial 100. As shown in FIG. 1A, zeolite nuclei 105 a, 105 b, 105 cwere aggregated around surfactant micelles under controlled conditionsto form a solid. Thereafter, the aggregated nuclei 105 a, 105 b, 105 cwere washed in water and dried and the surfactant was extracted toprovide a desired mesopore-sized pore volume 110, forming amorphousmesoporous zeolite nuclei material 100. Each of the zeolite nuclei, forexample, 105 a, 105 b, 105 c, is a nanosized crystal. When they areaggregated, the material 100 is polycrystalline because the nucleimaterial is lacking the long-range regular lattice structure of thecrystalline state (i.e., the aggregated nuclei are not fully crystallineor truly crystalline).

Some strategies have managed to improve appreciably the acidicproperties of Al-MCM-41 materials. However, due to the lack oflong-range crystallinity in these materials, their acidity is not asstrong as those exhibited by zeolites. For example, semicrystallinemesoporous materials, such as nanocrystalline aluminosilicate PNAs andAl-MSU-S_((MFI)), being even more active than conventional Al-MCM-41,showed significantly lower activity than H-ZSM-5 for cumene cracking;the catalyst activity for this reaction has usually been correlated tothe Bronsted acid strength of the catalyst.

Previous attempts to prepare mesostructured zeolitic materials have beenineffective, resulting in separate zeolitic and amorphous mesoporousphases. Moreover, some authors have pointed out the difficulty ofsynthesizing thin-walled mesoporous materials, such as MCM-41, withzeolitic structure, due to the surface tension associated with the highcurvature of the mesostructure.

SUMMARY OF THE INVENTION

One embodiment of the invention concerns a method of preparing a shapedzeolitic material with enhanced mesoporosity. The method of thisembodiment comprises: (a) forming a composite shaped article comprisingat least one zeolite and at least one non-zeolitic material; and (b)contacting the composite shaped article with at least one pH controllingagent and at least one surfactant under conditions sufficient toincrease the pore volume of at least one 10 angstrom subset ofmesoporosity in the composite shaped article, thereby forming the shapedzeolitic material with enhanced mesoporosity.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1a is a schematic diagram of a prior art polycrystalline mesoporousmaterial;

FIG. 1b is a schematic illustration of a fully crystallinemesostructured zeolite;

FIG. 1c depicts a transmission electron microscopy (“TEM”) image of ananostructured zeolite where the nanostructure shape includes nanorods;

FIG. 1d depicts the X-ray diffraction (“XRD”) pattern of a fullycrystalline mesostructured zeolite H—Y[MCM-41]. Both the orderedmesostructure MCM-41 (revealed by the XRD peaks at low angles) and theunmodified zeolitic fully crystalline structure H—Y are present;

FIG. 2 depicts the X-ray diffraction pattern of the fully crystallinemesostructured zeolite H-MOR[MCM-41]. Both the ordered mesostructureMCM-41 (revealed by the XRD peaks at low angles) and the unmodifiedzeolitic fully crystalline structure H-MOR are present;

FIG. 3 depicts the X-ray diffraction pattern of the fully crystallinemesostructured zeolite H-ZSM-5[MCM-41]. Both the ordered mesostructureMCM-41 (revealed by the XRD peaks at low angles) and the unmodifiedzeolitic crystalline structure H-ZSM-5 are present;

FIG. 4 depicts Fourier transform infrared spectroscopy (“FTIR”)characterization peaks for the fully crystalline mesostructured zeoliteH—Y[MCM-41], labeled Meso-H—Y, and the unmodified zeolite Y;

FIG. 5 depicts FTIR spectra of fully crystalline mesostructured zeolitesH—Y[MCM-41] (upper top), H-MOR[MCM-41] (upper middle), andH-ZSM-5[MCM-41] (upper bottom); and FTIR spectra of their unmodifiedfully crystalline zeolitic versions H—Y (lower top), H-MOR (lowermiddle), H-ZSM-5 (lower bottom). A match between each fully crystallinemesostructured zeolite and its corresponding unmodified zeolite isobserved, indicating the fully zeolitic connectivity present in thefully crystalline mesostructured zeolites;

FIG. 6 depicts the physisorption isotherm of N₂ at 77 K of a fullycrystalline mesostructured zeolite H—Y[MCM-41], labeled Meso-HY, and itsunmodified zeolitic version, H—Y. The pore size distribution (Barrett,Joyner, Halenda (“BJH”) method) of the fully crystalline mesostructuredzeolite is included in the inset. The presence of well developed narrowpore size mesoporosity in the mesostructured sample is evident by thesharp uptake at P/P₀˜0.3;

FIG. 7 depicts the physisorption isotherm of N₂ at 77 K of a fullycrystalline mesostructured zeolite H-MOR[MCM-41], labeled Meso-HMOR, andits unmodified zeolitic version, H-MOR. The pore size distribution (BJHmethod) of the fully crystalline mesostructured zeolite is included inthe inset. The presence of well developed narrow pore size mesoporosityin the mesostructured sample is evident by the sharp uptake at P/P₀˜0.3;

FIG. 8 depicts the physisorption isotherm of N₂ at 77 K of a fullycrystalline mesostructured H-ZSM-5[MCM-41], labeled Meso-HZSM5, and itsunmodified zeolitic version, HZSM5. The pore size distribution (BJHmethod) of the fully crystalline mesostructured zeolite is included inthe inset. The presence of well developed narrow pore size mesoporosityin the mesostructured sample is evident by the sharp uptake at P/P₀˜0.3;

FIG. 9 depicts pore volumes (darker columns) of fully crystallinemesostructured zeolites H—Y[MCM-41] (left), H-MOR[MCM-41] (center), andH-ZSM-5[MCM-41] (right) and their unmodified zeolitic versions (lightercolumns) of H—Y (left), H-MOR (center), and H-ZSM-5 (right);

FIG. 10a depicts images obtained by TEM of detail of an H—Y[MCM-41]fully crystalline mesostructured zeolite. The electron diffractionpattern is included as an inset;

FIG. 10b depicts images obtained by TEM of detail of an H—Y[MCM-41]fully crystalline mesostructured zeolite at different focus. Theelectron diffraction pattern is included as an inset;

FIG. 11 depicts a TEM image of a fully crystalline mesostructuredzeolite;

FIG. 12 depicts a TEM image of a fully crystalline mesostructuredzeolite;

FIG. 13 depicts a schematic illustration of catalytic cracking of1,3,5-triisopropyl benzene by an unmodified conventional zeolite H—Y;

FIG. 14 depicts a schematic illustration of catalytic cracking of1,3,5-triisopropyl benzene by a fully crystalline mesostructuredzeolite;

FIG. 15 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as conversion vs. time for a fully crystallinemesostructured zeolite H—Y[MCM-41], labeled Meso-HY, its unmodifiedzeolitic version HY, and a conventional AlMCM-41. A 50 mL/min stream ofHe saturated with 1,3,5-triisopropylbenzene at 120° C. was flowed at200° C. over 50 mg of catalyst;

FIG. 16 depicts the catalytic cracking of 1,3,5-triisopropyl benzenewith a fully crystalline mesostructured zeolite H—Y[MCM-41], labeledMeso-HY, to diisopropyl benzene and cumene. The H—Y[MCM-41] results arecompared to the normalized results from a commercial sample ofunmodified fully crystalline zeolite H—Y. Catalytic cracking with thefully crystalline mesostructured zeolite H—Y[MCM-41] results in higherselectivity and reduction in benzene production;

FIG. 17 depicts the hydrothermal stability of the fully crystallinemesostructured zeolite H—Y, H—Y[MCM-41], labeled Meso-HY, compared tothe conventional non-mesolytic zeolite Al-MCM-41;

FIG. 18 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as conversion vs. time for a fully crystallinemesostructured zeolite H-MOR[MCM-48], labeled Meso-HMOR, and itsunmodified zeolitic version H-MOR. A helium flow of 50 mL/min saturatedwith 1,3,5-triisopropylbenzene at 120° C. was introduced over 50 mg ofeach catalyst, H-MOR[MCM-48] and H-MOR, at 200° C.;

FIG. 19 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as conversion vs. time for a fully crystallinemesostructured zeolite H-ZSM-5[MCM-41], labeled Meso-H-ZSM-5, and itsunmodified zeolitic version H-ZSM-5. A helium flow of 50 mL/minsaturated with 1,3,5-triisopropylbenzene at 120° C. was introduced over50 mg of each catalyst, H-ZSM-5[MCM-41] and H-ZSM-5, at 200° C.;

FIG. 20a depicts, on the left-hand side Y axis, the conversion of1,3,5-triisopropylbenzene vs. time for the nanostructure H-MOR[ZNR] andthe unmodified fully crystalline zeolite H-MOR. The ratio of benzeneproduced by H-MOR-to-benzene produced by H-MOR[ZNR] as a function oftime is shown on the right-hand side Y axis. A helium flow of 50 mL/minsaturated with 1,3,5-triisopropylbenzene at 120° C. was introduced over50 mg of each catalyst, H-MOR[ZNR] and H-MOR, at 200° C.;

FIG. 20b depicts Microactivity test (“MAT”) results of a conventionalfully crystalline zeolite HY (Si/Al=15) and its fully crystallinemesostructured version HY[MCM-41];

FIG. 20c depicts the composition of the LPG fraction obtained by MAT ofa conventional fully crystalline zeolite HY (Si/Al=15) and its fullycrystalline mesostructured version HY[MCM-41];

FIG. 21 depicts the percentage of polyethylene (“PE”) weight lost vs.temperature for the mixtures of catalysts in weight ratio to PE labeled:(A): no catalyst; (B): H-ZSM-5:PE, 1:2; (C): H-ZSM-5[MCM-41]:PE, 1:2;(D): H-ZSM-5:PE, 1:1; (E) H-ZSM-5:PE, 2:1; (F): H-ZSM-5[MCM-41]:PE, 1:1;and (G) H-ZSM-5[MCM-41]:PE, 2:1;

FIG. 22 depicts the FTIR spectra of a) H—Y[MCM-41], b) NH₄—Y[MCM-41], c)NH₂(CH₂)₂NMe₃Cl, d) NH₂(CH₂)₂NMe₃-Y[MCM-41], d) Rh(PPh₃)₃Cl, and e)Rh(PPh₃)₃NH₂(CH₂)₂NMe₃-Y[MCM-41];

FIG. 23 depicts MAT yield results where a fully crystallinemesostructured zeolite HY[MCM-41] is employed as an additive to aconventional unmodified zeolite HY for fluid catalytic cracking of avacuum gas oil. The results from left to right on the X-axis show 100%HY with no additive, 10% HY[MCM-41] additive to the catalyst, 20%HY[MCM-41] additive to the catalyst, 50% HY[MCM-41] additive to thecatalyst, and 100% HY[MCM-41];

FIG. 24 depicts full XRD scans for the initial material prepared in theExample and a control sample, both described in Table 1, showing sharp,well defined peaks that are characteristic of well crystallized Yfaujasite zeolite;

FIG. 25 depicts the pore size distributions of the zeolitic microspheresprepared in the Example, both as-synthesized and after treatment toimpart mesoporosity;

FIG. 26 depicts the XRD pattern of the zeolitic microspheres withadditional mesoporosity (mesoporous in situ FCC), along with the XRDpatterns of untreated zeolitic microspheres (in situ FCC) and areference ultrastabilized Y zeolite (USY);

FIG. 27a is a scanning electron photomicrograph at 100× magnificationshowing the zeolitic microspheres having additional mesoporosity;

FIG. 27b is a scanning electron photomicrograph at 650× magnificationshowing a cross section of a zeolitic microsphere having additionalmesoporosity;

FIG. 27c is a scanning electron photomicrograph at 2,500× magnificationshowing a cross section of a zeolitic microsphere having additionalmesoporosity;

FIG. 27d is a scanning electron photomicrograph at 10,000× magnificationshowing a cross section of a zeolitic microsphere having additionalmesoporosity;

FIG. 27e is a scanning electron photomicrograph at 20,000× magnificationshowing a cross section of a zeolitic microsphere having additionalmesoporosity; and

FIG. 28 is electron photomicrograph of an individual zeolite crystalwithin a zeolitic microsphere having additional mesoporosity (in situFCC catalyst), particularly illustrating areas with the regular gridstructure of micropores that is characteristic of crystalline zeolite Yfaujasite, and also showing regions having a combination of the regulargrid structure and larger, less ordered pores of a larger size(mesopores).

DETAILED DESCRIPTION

Various embodiments of the present invention relate to a method ofenhancing the mesoporosity of inorganic materials having long-rangecrystallinity. Such inorganic materials can by prepared by treating aninitial inorganic material with a pH controlling agent and a surfactantunder time and temperature conditions. In one or more embodiments, theinitial inorganic material can constitute a portion of a compositeshaped article containing at least the inorganic material (e.g., azeolite) and at least one non-zeolitic material. The resulting inorganicmaterial with enhanced mesoporosity can have one or more of a variety ofmesostructures. Following formation, in various embodiments, themesostructured inorganic materials having enhanced mesoporosity can bevariously modified and/or employed in a variety of processes.

As noted above, an initial inorganic material can be employed in formingthe inorganic materials having long-range crystallinity and enhancedmesoporosity. In various embodiments, the initial inorganic material canhave a 1-dimensional, 2-dimensional, or 3-dimensional pore structure.Additionally, the initial inorganic material can itself exhibitlong-range crystallinity. Materials with long-range crystallinityinclude all solids with one or more phases having repeating structures,referred to as unit cells, that repeat in a space for at least 10 nm. Along-range crystalline inorganic material structure may have, forexample, single crystallinity, mono crystallinity, or multicrystallinity. Multi crystalline materials include all solids havingmore than one phase having unit cells that repeat in a space for atleast 10 nm. Furthermore, in various embodiments, the initial inorganicmaterial can be fully crystalline. Additionally, the initial inorganicmaterial can be a one-phase hybrid material. Examples of inorganicmaterials suitable for use as the initial inorganic material include,but are not limited to, metal oxides, zeolites, zeotypes,aluminophosphates, gallophosphates, zincophosphates, andtitanophosphates. Combinations of two or more types of these inorganicmaterials can also be employed as the initial inorganic material. Inaddition, the inorganic material can be a zeolite-like material, whichrepresents a growing family of inorganic and organic/inorganic molecularsieves. In one or more embodiments, the initial inorganic materialcomprises a zeolite. Examples of zeolites suitable for use as theinitial inorganic material include, but are not limited to, faujasite(a.k.a., zeolite Y; “FAU”), mordenite (“MOR”), ZSM-5 (“MFI”), and CHA.Additionally, ultra-stable (e.g., zeolite USY) and/or acid forms ofzeolites can also be employed. In various embodiments, the initialinorganic material can comprise faujasite, mordenite, ZSM-5, or mixturesof two or more thereof. In various embodiments, the initial inorganicmaterial comprises faujasite.

In one or more embodiments, the initial inorganic material can bepresent as a part of a composite shaped article comprising at least oneinorganic material (e.g., a zeolite) and at least one non-zeoliticmaterial. In one or more embodiments, the inorganic material in thecomposite shaped article can be a zeolite. Furthermore, the inorganicmaterial can comprise a zeolite selected from the group consisting offaujasite, mordenite, ZSM-5, CHA, or mixtures of two or more thereof. Invarious embodiments, the zeolite comprises faujasite. The compositeshaped article can comprise the inorganic material (e.g., a zeolite) inan amount of at least 0.1 weight percent, at least 15 weight percent, orat least 30 weight percent based on the total weight of the compositeshaped article. Furthermore, the composite shaped article can comprisethe inorganic material (e.g., a zeolite) in an amount in the range offrom about 0.1 to about 99 weight percent, in the range of from about 5to about 95 weight percent, in the range of from about 15 to about 70weight percent, or in the range of from 30 to 65 weight percent based onthe total weight of the composite shaped article.

In various embodiments, the non-zeolitic material of the compositeshaped article can comprise one or more components selected from thegroup consisting of inert stable oxides, inert stable carbides, inertstable nitrides, and mixtures of two or more thereof. Examples of inertstable oxides suitable for use include, but are not limited to,alpha-aluminum oxide, titanium dioxide, zirconium oxide, mullite,hydrous kaolin clay, and the residue of alkaline extraction of kaolinclay which has been calcined through the characteristic exotherm atabout 1,780° F. without substantial formation of mullite. An example ofan inert stable carbide includes, but is not limited to, siliconcarbide. An example of an inert stable nitride includes, but is notlimited to, silicon nitride. In other various embodiments, thenon-zeolitic material of the composite shaped article can comprise asubstantially insoluble alkaline oxide, such as, for example, magnesiumoxide or calcium oxide. In one or more embodiments, the composite shapedarticle can have a total non-zeolitic material content of at least 15,at least 30, or at least 35 weight percent based on the total weight ofthe composite shaped article. Furthermore, the composite shaped articlecan have a total non-zeolitic material content in the range of fromabout 1 to about 99.9 weight percent, in the range of from about 5 toabout 95 weight percent, in the range of from about 30 to about 85weight percent, or in the range of from 35 to 70 weight percent based onthe total weight of the composite shaped article.

The composite shaped article can be formed by a variety of methods. Invarious embodiments, the composite shaped article can be formed by firstcombining the non-zeolitic material with at least one zeolitic materialto form an initial mixture. The zeolitic and non-zeolitic materials canbe present in the initial mixture in amounts described above for thecomposite shaped article. Thereafter, the initial mixture can be shapedinto the composite shaped article.

Alternatively, the composite shaped article can be prepared by (i)combining the non-zeolitic material and/or a precursor of thenon-zeolitic material with a zeolite precursor to form an initialmixture; (ii) shaping the initial mixture into an initial compositeshaped article; and (iii) converting at least a portion of the zeoliticprecursor in the initial composite shaped article into a zeolite therebyforming the composite shaped article. Suitable zeolite precursorsinclude, but are not limited to, hydrous kaolin clay, metakaolin, sodiumsilicate, and sodium aluminate, any of which or a combination thereofmay be employed in forming the initial mixture of step (i). Aftershaping the initial mixture, the initial composite shaped article can betreated under any conditions suitable for converting at least a portionof the zeolite precursors into zeolitic material. For example, theinitial composite shaped article can be calcined at temperatures rangingfrom about 1,000 to about 1,400° F., or from 1,100 to 1,300° F. Invarious embodiments, the calcined material can combined with additionalzeolite precursors in a basic solution (e.g., a sodium hydroxidesolution). The resulting mixture can be heated (e.g., from 100 to 300°F., or about 210° F.) while stirring for a time period in the range offrom about 1 hour to about 1 week, in the range of from 12 hours to 2days, or about 24 hours. Thereafter, the material can be filtered,washed with deionized water, and dried (e.g., at about 80° C.).

Regardless of the method employed, the initial mixture can be shapedinto any desired shape suitable for the intended use of the finalproduct. In various embodiments, the composite shaped article can have ashape selected from the group consisting of a pellet, a tablet, amicrosphere, a bead, a honeycomb shape, or mixtures of two or morethereof. Any method known or hereafter discovered in the art can beemployed for shaping the initial mixture. For example, the mixture canbe shaped by extruding, molding, spray drying, pelletizing, orcombinations thereof. In one or more embodiments, microspheres can beformed by spray drying the initial mixture. Once the material is shaped,it can be aged by, for example, being treated in air at a temperatureranging from, for example, about 10 to about 200° C. The shaped materialcan be treated for a time ranging from about 1 hour to about 1 week.Optionally, it can be heat treated a second time at a highertemperature. The second temperature can vary from about 200 to about800° C. and for a time period from about 1 hour to about 1 week.

In various embodiments, the composite shaped article can be a FluidCatalytic Cracking (“FCC”) catalyst. As known to those of ordinary skillin the art, FCC catalysts typically contain a molecular sieve (e.g., azeolite such as faujasite), a binder, a filler, and a matrix. Thus, invarious embodiments, the composite shaped article can contain variousother components known or hereafter discovered by those skilled in theart of FCC catalysis. FCC catalysts suitable for use as the compositeshaped article include any known or hereafter discovered FCC catalysts.In various embodiments, the FCC catalyst can be a faujasite-containingcatalyst.

In various embodiments, the initial inorganic material can be treated toalter a portion of the chemical structure of the initial inorganicmaterial. For example, the inorganic material can be initially treatedwith an acid, such as hydrofluoric acid, which can dissolve a portion ofsilica in a zeolite and soften the structure. For instance, very stablezeolites having dense structures (e.g., ZSM-5) may benefit frompretreatment with acid. In other various embodiments, when a zeolite ora composite shaped article is employed as the initial inorganicmaterial, it can be treated to extract a portion of the aluminum fromthe zeolite. Suitable methods for aluminum removal include, but are notlimited to, acid extraction, acid extraction with a chelating acid(e.g., citric acid), chelating agent extraction (such as with ethylenediamine tetra-acetic acid (“EDTA”)), SiCl₄ vapor treatment, andtreatment with (NH₄)₂SiF₆. In various embodiments, aluminum extractioncan be performed by contacting the initial inorganic material with anacid and/or a chelating agent. In various embodiments, when the initialinorganic material contains a zeolite having a SiO₂/Al₂O₃ ratio belowabout 20, the initial inorganic material undergoes aluminum extraction.

In cases where pretreatment for aluminum extraction is practiced,composite shaped articles can be formulated so as to be resistant todegradation by the pretreatment process. This can maintain good physicalproperties in the shaped article and may prevent excessive aluminumextraction from non-zeolitic constituents. If an excessive amount ofaluminum is removed from the non-zeolitic constituents of the shapedarticle, it can result in increased chemical and processing costs toachieve adequate removal of aluminum from the zeolite constituents. Thisis in addition to the potential for weakening of the non-zeoliticmaterial as a result of acid attack.

As a result of the potential for increased cost or degradation of theshaped article during either an aluminum extraction step or during theprocess of mesoporosity creation, the non-zeolitic material of theshaped article selected can be resistant to chemical attack under thechosen processing conditions. For example, when extracting aluminum witheither an acid or a chelating acid, the non-zeolitic material can beselected based on its degree of resistance to degradation by acidattack, and also to aluminum removal by acid attack. Similarly, underalkaline conditions, such as may be used for mesoporosity creation(discussed below), there is potential for alkali attack upon thenon-zeolitic material in the composite shaped article. Thus, thenon-zeolitic material may be selected based on its degree of resistanceto alkaline attack. In both cases, the term “resistant” means that thematerial is not degraded to an unacceptable degree. It is not necessarythat “resistant” materials be completely unaffected by the respectivechemical conditions.

Examples of materials that are resistant to both acidic and alkalinechemical attack include, but are not limited to, inert stable oxides,such as alpha-aluminum oxide, titanium dioxide, zirconium oxide,mullite, hydrous kaolin clay, and the residue of alkaline extraction ofkaolin clay which has been calcined through the characteristic exothermat about 1780° F. without substantial formation of mullite; inert,stable carbides, such as silicon carbide; and inert stable nitrides,such as silicon nitride. Examples of materials resistant to alkalinechemical attack but not acidic attack include, but are not limited to,substantially insoluble alkaline oxides, such as magnesium oxide andcalcium oxide.

As noted above, the initial inorganic material can be treated with a pHcontrolling agent in a pH controlled medium. In one or more embodiments,the pH controlling agent can comprise an acid or a base. In variousembodiments, the pH controlling agent comprises a base. Any base can beemployed and in any concentration that produces a desired pH range inthe pH controlled medium. In various embodiments, the pH controlledmedium can have a pH in the range of from about 8 to about 12, in therange of from 9 to 11, or about 10. In other embodiments, the pHcontrolled medium can have a pH in the range of from about 10 to about14, in the range of from 11 to 13, or about 12. Examples of basessuitable for use as the pH controlling agent include, but are notlimited to, ammonium hydroxide, a tetraalkylammonium hydroxide (e.g.,tetramethylammonium hydroxide), and sodium hydroxide. In variousembodiments, the pH controlled medium can further comprise water, suchthat the pH controlling agent is employed as an aqueous solution.

In other embodiments, the pH controlling agent comprises an acid. Anyacid can be employed and in any concentration that produces a desired pHrange in the pH controlled medium. In various embodiments the pHcontrolled medium can have a pH in the range of from about 2 to about 6,in the range of from 3 to 5, or about 4. In other embodiments, the pHcontrolled medium can have a pH in the range of from about −2 to about2, in the range of from −1 to 1, or about 0. Examples of acids suitablefor use as the pH controlling agent include, but are not limited to,hydrofluoric acid and hydrochloric acid. It should be noted that acidsmay be of particular use when the initial inorganic material selectedfor use is a very stable zeolite, such as, for example, ZSM-5,mordenite, or CHA, as discussed above. In various embodiments, theinitial inorganic material can first be treated in a pH controlledmedium having a low pH for an initial time period. Thereafter, the pH ofthe pH controlled medium can be increased by adding a base, such asthose described above, to increase the pH, such as to the rangesdescribed above.

As noted above, the initial inorganic material can also be treated witha surfactant. The order of addition of the surfactant is not critical.In various embodiments, the surfactant can be present in the pHcontrolled medium prior to introducing the initial inorganic material.In other embodiments, the surfactant can be added to the pH controlledmedium following addition of the initial inorganic material. In stillother embodiments, a first portion or a first surfactant can be presentat the time when the initial inorganic material is introduced and,thereafter, a second portion and/or a second surfactant can be added tothe medium.

Surfactants suitable for use can be cationic, anionic, or neutral. Invarious embodiments, the surfactant comprises a cationic surfactant. Inother embodiments, the surfactant comprises an anionic surfactant, aneutral surfactant, or a combination of these. Though not wishing to bebound by theory, it is believed that selection of the surfactant mayaffect the character of the mesopores introduced into the inorganicmaterial. For instance, surfactants with larger substituents (such aslonger pendant alkyl chains) may produce larger mesopores in theinorganic material. Specific examples of surfactants suitable for useinclude, but are not limited to, alkylammonium halides (e.g.,cetyltrimethylammonium bromide (“CTAB”)) and PLURONIC® (available fromBASF, Florham Park, N.J.). In certain embodiments, when the pHcontrolled medium has a basic pH (e.g., from about 8 to about 14, orfrom 9 to 12), the surfactant employed can comprise a cationicsurfactant, such as CTAB. In other embodiments, when the pH controlledmedium has an acidic pH (e.g., from about −2 to about 6, about −2 toabout 2, or about 0), the surfactant employed can comprise an anionicsurfactant and/or a neutral surfactant, such as PLURONIC®.

The quantity of surfactant employed can be varied according to the typeof surfactant employed and the type of initial inorganic materialemployed. In various embodiments, the surfactant can be present in aweight ratio with the initial inorganic material in the range of fromabout 0.01:1 to about 10:1, in the range of from about 0.5:1 to about2:1, or of about 1:1 surfactant-to-inorganic material based on thecombined weight of the surfactant and the initial inorganic material. Invarious embodiments, the weight of surfactant employed can be about halfthe weight of the initial inorganic material employed.

In addition to a surfactant, the pH controlled medium can optionallycomprise one or more additional reagents. For example, a swelling agent,nanoparticles, biomolecules, a mineralizing agent, a co-surfactant, ametal oxide precursor, a silica solubilizing agent, an aluminasolubilizing agent, a triblock copolymer, or any combination thereof,can be added to the pH controlled medium before and/or afterintroduction of the inorganic material. Such reagents can be selected tocontrol a cross-sectional area of each of a plurality of mesoporesintroduced into the inorganic material. For instance, use of a swellingagent can expand the surfactant micelles, thereby resulting in largermesopore formation in the inorganic material.

When contacting the initial inorganic material with a pH controlledmedium and a surfactant, any time and temperature conditions can beemployed that permit mesopore introduction in the initial inorganicmaterial (e.g., the composite shaped article). Generally, the time andtemperature conditions are related such that a higher temperaturerequires a shorter period of time to achieve a desired mesoporosity inthe inorganic material resulting in a certain mesostructure. Conversely,a lower temperature may require a relatively longer period of time toachieve the same mesoporosity. Additionally, selection of time andtemperature conditions can affect the type of mesostructure that iscreated in the inorganic material. Thus, by adjusting the synthesisconditions (e.g., pH, time, temperature, inorganic material type,surfactant concentration) different mesostructures (e.g., MCM-41,MCM-48, and MCM-50) can be produced. Because time and temperature arerelated, any suitable combination of time and temperature may beemployed when treating the mixture. For example, the temperature canrange from a value in the range of from about room temperature to about60° C. In other embodiments, the temperature can be in the range of fromabout 60 to about 100° C., in the range of from 70 to 90° C., or about80° C. In still other embodiments, the temperature employed can be inthe range of from about 100 to about 200° C., in the range of from 100to 150° C., or about 120° C. In yet other embodiments, the temperaturecan have a value of at least 100° C.

The time period employed for treatment of the inorganic material can bein the range of from about one hour to about two weeks. In otherembodiments, the mixture described above can be held at room temperatureand stirred for a time value within the range of from about 1 day toabout 1 week. Alternatively, the mixture can be treated for a timeperiod in the range of from about 4 hours to about 1 week.

In one or more embodiments, the controlled time and temperatureconditions can take place under hydrothermal conditions, such as, forexample, in a sealed reactor where autogenous pressure is created withinthe sealed reactor. During hydrothermal treatment, the mixture can bestirred by, for example, rotating the vessel (i.e., rotating a sealedreactor or an autoclave). Alternatively or in addition, the contents ofthe vessel can be stirred by employing one or more stirrers inside thevessel to stir the mixture during the hydrothermal treatment. Stirringthe mixture can help avoid sedimentation and may improve distribution ofthe mixture within the vessel.

In various embodiments, when all or a portion of the surfactant is addedto the pH controlled medium after the inorganic material has been added,treatment of the inorganic material can be done at differenttime/temperatures. For example, in various embodiments, an inorganicmaterial can be treated in a pH controlled medium optionally containinga surfactant under a first set of time/temperature conditions.Thereafter, surfactant can be added to the mixture and the inorganicmaterial can be treated under a second set of time/temperatureconditions. Any of the time and temperature conditions described abovemay be used in such a multi-stage treatment process. Additionally, anyof the foregoing process steps can be repeated as desired.

In various embodiments, the treatment described above can allow theinitial inorganic material to form a plurality of mesopores having acontrolled cross sectional area forming a mesostructure havinglong-range crystallinity. Suitable mesostructures include, but are notlimited to, hexagonal, cubic, lamellar, foam, random, organized, andcontrolled. For example, an H—Y[MCM-41] is a mesostructure of an acidicform of faujasite (i.e., H—Y) having long-range crystallinity and havinga hexagonal mesopore arrangement (i.e., [MCM-41]). Similarly, anH—Y[MCM-48] is a mesostructure of an acidic form of faujasite havinglong-range crystallinity and having a cubic pore arrangement. Also, anH—Y[MCM-50] is a mesostructure of an acidic form of faujasite havinglong-range crystallinity and having a lamellar pore arrangement.

The treated inorganic material (a.k.a., the mesostructured material(e.g., a fully crystalline mesostructured zeolite)) described above canundergo a variety of post-synthesis treatments. For example, steps formaking a mesostructured material may be repeated or cycled to obtain adesired result. One or more of the hydrothermal treatment conditions,surfactant type, surfactant quantity, and the pH of the pH controlledmedium may be altered in each successive cycle. For example, a treatedinorganic material still present in the synthesis solution may behydrothermally treated one or more additional times. Specifically, afterhydrothermal treatment in the pH controlled media in the presence ofsurfactant and prior to other post-synthesis steps (e.g., filtration,drying, and calcination), one or more of the hydrothermal treatment,surfactant type, surfactant quantity, and pH may be altered in one ormore subsequent cycles. Cycles may be employed to further improve theamount, quality, and ordering of the mesoporosity introduced in theinorganic material. Synthesis parameters such as, for example, pH,concentration of surfactant, water content, and mineralization agents,can be adjusted prior to successive hydrothermal treatment. Variouscycles of hydrothermal treatment and parameter synthesis can be used. Invarious embodiments, a fully crystalline mesostructured zeolite can beformed in between about 1 and about 10 cycles, for example. In eachcycle, the hydrothermal temperature can vary from about 50 to about 200°C., and the time period allowed for synthesis can vary from about 2hours to about 2 weeks. Other time and temperatures described above forthe initial treatment may also be used.

In various embodiments, after a first hydrothermal treatment, theresulting slurries having an initial pH in the range from about 8 toabout 14 can be partially neutralized to a final pH of from about 8 toabout 10 by employing acids. Acids suitable for use can be mineral ororganic and include, for example, HCl, HNO₃, H₂SO₄, HF, acetic acid, orany combination of such acids. The quantity of surfactant including, forexample, quaternary ammonium, phosphonium based surfactants, cationic,neutral or anionic surfactants, can be increased from about 5 to about500%. In a second cycle, the same surfactant from the first cycle may beemployed. Alternatively, in a second cycle, a second differentsurfactant or any combination of surfactants may be employed.

In an exemplary synthesis, a zeolite H—Y (Si/Al˜15) was hydrothermallytreated in a sodium hydroxide solution having a pH of 11 and containingthe surfactant CTAB at a zeolite-to-CTAB ratio of 1 at 120° C. for 12hours. After this treatment 0.2 cc/g of mesoporosity was introduced inthe original zeolite, as measured by nitrogen adsorption at 77 K. Poresize distribution was fairly narrow and no mesopore ordering wasobserved under Transmission Electron Microscopy (“TEM”). In a secondcycle, 1.0 M HCl was added until the pH reached 9, an excess of 50% ofCTAB surfactant was added to provide a zeolite to CTAB ratio of 1 to1.5, and second hydrothermal treatment at 120° C. for a 12 hoursproduced a 0.3 cc/g mesopore volume, a narrower pore size distribution,and same local mesopore ordering, observed by TEM. The materials asmodified by changing synthesis parameters and hydrothermal conditionswere characterized by X-ray diffraction, gas adsorption, and electronicmicroscopy. These techniques confirmed that it is possible to control ofthe synthesis conditions even after some mesoporosity is introduced inthe inorganic material. In addition, the successive hydrothermaltreatments enable controlled mesoporosity (i.e., controlled pore volume,controlled pore size, and/or controlled pore shape) in themesostructured material (e.g., a fully crystalline mesostructuredzeolite).

Following treatment with the pH controlling agent and the surfactant,the resulting treated inorganic material (which can be a mesostructurehaving long-range crystallinity) can be separated from the reactionmedium. In various embodiments, the step of separating themesostructured material from the reaction medium can be carried out byone or more methods selected from the group consisting of filtration,centrifugation, and sedimentation. Following separation, the treatedinorganic material can be washed and dried. For example, the treatedinorganic material can be washed once or repeatedly with water (e.g.,deionized water). Additionally, the treated inorganic material can bedried at an elevated temperature. As used herein, the term “elevatedtemperature” is intended to denote any temperature greater than roomtemperature. For example, the treated inorganic material can be dried ata temperature in the range of from about 50 to about 100° C.

After separation, washing, and drying, at least a portion of anyremaining surfactant can be removed by, for example, calcination orsurfactant extraction. In one or more embodiments, the treated inorganicmaterial can initially be calcined in nitrogen at a maximum temperaturefrom about 500 to 760° C. (or about 1,000 to about 1,400° F.), or atabout 550° C.; and then in air for surfactant removal. In variousembodiments, the surfactant removal technique can be selected based, forexample, on the time needed to remove all or substantially all of thesurfactant from the treated inorganic material. In other variousembodiments, residual surfactant can be removed via contacting thetreated inorganic material with one or more extraction agents underconditions of time and temperature sufficient to extract at least aportion of the residual surfactant. Extraction agents can include, butare not limited to, solvents, acid/solvent mixtures, supercriticalfluids, or mixtures thereof. Solvents suitable for use as extractingagents either alone or in combination with an acid include, but are notlimited to, an alcohol (e.g., methanol, ethanol, and isopropyl alcohol),acetone, dimethylformamide, methylpyrrolidone, a halogenated solvent,acetonitrile, and mixtures of two or more thereof. Acids suitable foruse in an acid/solvent extraction agent include, but are not limited to,inorganic acids, such as hydrochloric acid, nitric acid, or sulphuricacid; organic acids, such as a sulphonic acid, a carboxylic acid, or ahalogenated acid; and mixtures of two or more thereof. Supercriticalfluids suitable for use as extraction agents include, but are notlimited to, carbon dioxide, an alcohol, ammonia, a halogenated methane,a halogenated hydrocarbon, and mixtures of two or more thereof. Whetherby calcination and/or extraction agent, in the range of from about 65 toabout 100, in the range of from about 75 to about 90, or about 80 weightpercent of the surfactant can be removed from the treated inorganicmaterial.

When the initial inorganic material employed is a composite shapedarticle as described above, the above-described process can besufficient to increase the pore volume of at least one 10 angstromsubset of mesoporosity in the composite shaped article, thereby forminga shaped zeolitic material with enhanced mesoporosity. As used herein, a“subset of mesoporosity” refers to a sub-range of pore sizes within the20 to 600 angstrom range. Thus, a “10 angstrom subset of mesoporosity”could be any 10 angstrom range of pore sizes between 20 and 600angstroms (e.g., 22-32; 40-50; 135-145; or 499-509 angstroms). All thatis required “to increase the pore volume of at least one 10 angstromsubset of mesoporosity,” as stated above, is for there to exist at leastone 10 angstrom range of pore sizes between 20 and 600 angstroms thatincreases in volume, even if the net mesoporosity over the entire 20 to600 angstrom range stays the same or decreases. In various embodiments,the increase in pore volume of the 10 angstrom subset can constitute anincrease of at least 0.01, at least 0.04, or at least 0.08 cc/g in that10 angstrom subset. Additionally, the increase in pore volume of the 10angstrom subset can constitute an increase of at least 10, 20, 30, 40,50, 60, 70, 80, 90, 100 or more percent of the pore volume of the 10angstrom subset. In one or more embodiments, the selected 10 angstromsubset can be contained within a broader range of from 20 to 250angstroms, from 20 to 80 angstroms, or from 30 to 70 angstroms. Invarious embodiments, the conditions employed during the above-describedprocess can be sufficient to increase the pore volume of at least one 25angstrom subset of mesoporosity in the composite shaped article. Instill other embodiments, the conditions employed during theabove-described process can be sufficient to increase the pore volume ofat least one 50 angstrom subset of mesoporosity in the composite shapedarticle.

Additionally, when the initial inorganic material is a composite shapedarticle, the treatment described above can cause the formation of aplurality of intracrystalline mesopores in the zeolite of the compositeshaped article. As used herein, the term “intracrystalline” is intendedto denote that the additional mesoporosity is located within thezeolite, as opposed to the non-zeolitic material. Additionally, invarious embodiments, the treatment described above can cause a netincrease in the overall mesoporosity of the composite shaped article.For example, treatment as described above can cause a net increase inthe mesoporosity of at least 0.01, at least 0.05, or at least 0.1 cc/gin the zeolite and/or the non-zeolitic material in the composite shapedarticle. Furthermore, treatment as described above can cause a netincrease of at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 100 or morepercent in the overall mesoporosity of the composite shaped article. Theresulting shaped zeolitic material having enhanced mesoporosity can havea total volume of mesopores in the range of from about 0.05 to about 0.9cc/g, or in the range of from 0.1 to 0.8 cc/g.

As noted above, the resulting treated inorganic material can be in theform of a mesostructure. Furthermore, when the initial inorganicmaterial comprises a zeolite, the treated inorganic material can be amesostructured zeolite. The hybrid structure of mesostructured zeoliteswas studied via X-ray diffraction (“XRD”). FIGS. 1d -3 show the XRDpatterns of H—Y[MCM-41], H-MOR[MCM-41], and H-ZSM-5[MCM-41],respectively. As used herein, the naming convention for mesostructuredzeolites (e.g., H—Y[MCM-41]) first includes the starting zeolitestructure (e.g., H—Y) and then, placed adjacent in brackets, is the nameof the mesostructure (e.g., [MCM-41]). The mesostructured zeoliteH—Y[MCM-41] retains the full crystallinity of the zeolite H—Y, andfeatures hexagonal pores [MCM-41]. The fully crystalline mesostructuresurrounds these hexagonal mesopores that have been formed by theinvention. Thus, the resulting structure is a fully crystalline H—Ymaterial that features an [MCM-41] type of mesostructure. Forconvenience, this is designated as H—Y[MCM-41].

FIG. 1d depicts the X-ray diffraction pattern of the mesostructuredzeolite H—Y[MCM-41], and both the ordered mesostructure MCM-41 (revealedby the XRD peaks at low angles) and the zeolitic fully crystallinestructure H—Y are present. FIG. 2 depicts the X-ray diffraction patternof the mesostructured zeolite H-MOR[MCM-41], and both the orderedmesostructure MCM-41 (revealed by the XRD peaks at low angles) and thezeolitic crystalline structure H-MOR are present. FIG. 3 depicts theX-ray diffraction pattern of the mesostructured zeolite H-ZSM-5[MCM-41],and both the ordered mesostructure MCM-41 (revealed by the XRD peaks atlow angles) and the zeolitic crystalline structure H-ZSM-5 are present.Referring now to FIGS. 1d -3, very intense peaks, both at low and high2°Θ values, reveal both the ordered mesostructure and the zeoliticcrystallinity of this family of materials. In all three cases, the peaksat low 2°Θ values can be indexed to hexagonal symmetry indicating thepresence of MCM-41, whereas the well-defined XRD peaks at high 2° Θvalues correspond, respectively, to the zeolites Y, MOR and ZSM-5. Thisobservation is remarkable since no long-range crystallinity has beenpreviously observed in mesoporous metal oxides and onlysemicrystallinity (due to the presence of zeolite nanoclusters) has beenachieved in thick-wall mesoporous materials prepared using triblockcopolymers.

The connectivity of the mesostructured zeolites was studied by Fouriertransform infrared spectroscopy (“FTIR”), the results of which are shownin FIGS. 4-5. FIG. 4 depicts FTIR characterization peaks for the fullycrystalline mesostructured zeolite H—Y[MCM-41] and zeolite H—Y. The FTIRspectra of the fully crystalline mesostructured zeolite H—Y[MCM-41],labeled Meso-H—Y, is on the top, and the FTIR spectra of the unmodifiedconventional fully crystalline zeolite H—Y is on the bottom. FIG. 5depicts FTIR spectra of H—Y[MCM-41] (upper top), H-MOR[MCM-41] (uppermiddle), H-ZSM-5[MCM-41] (upper bottom), and FTIR spectra of their fullycrystalline zeolitic versions in conventional, unmodified form, H—Y(lower top), H-MOR (lower middle), H-ZSM-5 (lower bottom). The spectraof the fully crystalline mesostructured zeolite H—Y[MCM-41] is the uppertop spectra and the spectra of the unmodified fully crystalline zeoliteH—Y is the lower top spectra. The spectra of the fully crystallinemesostructured zeolite H-MOR[MCM-41] is the upper middle spectra and thespectra of the unmodified fully crystalline zeolite H-MOR is the lowermiddle spectra. The spectra of the fully crystalline mesostructuredzeolite H-ZSM-5[MCM-41] is the upper bottom spectra and the spectra ofthe unmodified fully crystalline zeolite H-ZSM-5 is the lower bottomspectra. In FIG. 5 a match between each fully crystalline mesostructuredzeolite and its corresponding unmodified fully crystalline zeolite isobserved, indicating the zeolitic connectivity is present in fullycrystalline mesostructured zeolites. FIG. 5 shows a remarkable matchbetween the IR spectra of the fully crystalline mesostructured zeolitesH—Y[MCM-41], H-MOR[MCM-41], and H-ZSM-5[MCM-41] and those of the theircorresponding unmodified fully crystalline zeolitic versions, H—Y,H-MOR, H-ZSM-5, contrary to highly stable Al-MCM-41, which presents onlyone IR broad peak, due to imperfect zeolitic connectivity. The peak at960 cm⁻¹ in the H—Y[MCM-41] mesostructured zeolite sample,characteristic of silanol groups on the wall surfaces, providesadditional evidence of the mesoporous/zeolitic hybrid nature ofmesostructured zeolites.

The presence of well-defined mesoporosity in mesostructured zeolites canbe suitably studied by nitrogen physisorption at 77 K. FIGS. 6-8 showthe nitrogen isotherms at 77 K of fully crystalline mesostructuredzeolites H—Y[MCM-41], H-MOR[MCM-41], and H-ZSM-5 [MCM-41], respectively,and their unmodified zeolitic versions, H—Y, H-MOR, and H-ZSM-5. Thepresence of well developed narrow pore size diameter distributionmesoporosity is evident in each mesostructured sample. The pore size ofthe mesoporosity is controlled such that a diameter and/or a crosssectional area of each of the mesopores in a specific fully crystallinemesostructured zeolite falls within a narrow pore size diameterdistribution. In one or more embodiments, more than 95% of the mesoporeshave a pore size (e.g., a diameter and/or a cross sectional area) thatfalls within plus or minus 75%, 30%, or 10% of the average pore size.Each pore wall or mesopore surface that surrounds a diameter controlledmesopore can be substantially similar in size. Furthermore, the fullycrystalline mesostructured zeolites can have a controlled mesoporositypore size cross sectional area. Where the mesopores are substantiallycylindrical in shape in addition to having a pore size cross sectionalarea, these pores have a pore size diameter. However, where the shape ofthe mesopores are not cylinder-like and are, for example, slit shaped,worm-like (e.g., with a changing diameter throughout at least a portionof the depth of the mesopore surface that surrounds an exemplarymesopore), or non-defined shapes, then at least a portion of such amesopore surface can have a controlled mesopore cross sectional area.The size of the mesopores is controlled by, for example, the selectedsurfactant and/or quantity of surfactant used when making a fullycrystalline mesostructured zeolite from a conventional unmodified fullycrystalline zeolite. Prior attempts to incorporate mesostructures intozeolites have been unable to achieve such a controlled mesoporosity thatresults in substantially all mesopores in a zeolite having asubstantially similar size (e.g., diameter and/or cross sectional area)and a controlled pore arrangement (e.g., [MCM-41] having a hexagonalpore arrangement). Rather, prior attempts to form mesostructures inzeolites have resulted in any or a combination of a broader pore sizedistribution ranging from small, medium, to large size pores, differentshaped pores, and uncontrolled arrangements.

In various embodiments, a significant volume of mesoporosity can beintroduced into the initial inorganic material. For example, referringto FIG. 6, the mesopore volume roughly doubles when the zeolite ismesostructured. In accordance with principles of the invention, in thesample of FIG. 6, the unmodified zeolite H—Y had a mesopore volume of0.30 cc/g whereas the fully crystalline mesostructured zeolite labeledMeso-HY, which was H—Y[MCM-41], had a mesopore volume of 0.65 cc/g.Conventional zeolites adsorb nitrogen only at low pressures, producingtype I isotherms that are characteristic of microporous materials.However, fully crystalline mesostructured zeolites show sharp nitrogenuptakes at higher partial pressures (e.g., P/P₀˜0.3), which is acharacteristic feature of mesostructured materials with narrow pore-sizedistribution (pore diameter˜2.5 nm). FIGS. 6-8 show similar results forfully crystalline mesostructured zeolites H—Y[MCM-41], H-MOR[MCM-41],and H-ZSM-5[MCM-41], and their unmodified conventional zeolitic versionsH—Y, H-MOR, and H-ZSM-5.

FIG. 9 depicts mesostructured zeolite pore volumes (darker columns) ofH—Y[MCM-41] (left), H-MOR[MCM-41] (center), and H-ZSM-5 [MCM-41] (right)and their zeolitic versions (lighter columns) of H—Y (left), H-MOR(center), and H-ZSM-5 (right). As seen in FIG. 9, compared toconventional zeolites, the fully crystalline mesostructured zeoliteshave more than double the pore volume due to the incorporation of awell-developed, narrow distribution of pore-size diameter mesoporosity.Referring still to FIG. 9, the volume of mesoporosity that isincorporated can be controlled. The fully crystalline mesostructuredzeolite mesoporosity volume can be controlled by, for example, thequantity of surfactant added as a percentage of the quantity of zeolite.Other factors that contribute to mesoporosity volume include the pH,time, and temperature conditions employed. In one or more embodiments,the volume of the controlled pH medium that is added can be an amountsuitable to achieve the desired surfactant concentration in view of theamount of zeolite. The pore volume is expressed in cubic centimeters ofpores over the grams of the zeolite (“cc/g”). The fully crystallinemesostructured zeolite pore volume can be in the range of from about0.05 cc/g to about 2 cc/g, or from about 0.5 cc/g to about 1 cc/g. Themesopore size is controlled and the mesopore volume can be controlled,at least in part, by the type and the quantity of surfactant used tocreate the zeolite mesostructure from the zeolite. The time andtemperature conditions may also contribute to the mesopore size and/orthe mesopore volume.

In various embodiments, the treated inorganic material prepared asdescribed above can retain substantially the same exterior surfacecontour (e.g., has substantially the same external size and externalshape) and cover substantially the same perimeter as the unmodifiedinitial inorganic material. When the initial inorganic material is azeolite, suitable unmodified conventional zeolites may range in sizefrom about 400 nm to about 5 microns. In one or more embodiments, theconditions employed to form the mesopores can be selected so as to notsubstantially change the external size, external shape or the perimeterof the unmodified zeolite. When a zeolite is employed as the initialinorganic material, the density of the resulting fully crystallinemesostructured zeolite can be less than the density of the unmodifiedzeolite; the density difference may be due to the zeolite removed whenthe mesopores were formed. In addition, where the fully crystallinemesostructured zeolite is produced from a fully crystalline conventionalunmodified zeolite, the fully crystalline mesostructured zeolite canmaintain the full crystallinity of the unmodified conventional zeolite.

Where the unmodified conventional zeolite has a chemical composition inits framework, after mesopores are formed in the conventional zeolite,the chemical composition in the resulting fully crystallinemesostructured zeolite framework can remain substantially the same asthe chemical composition in the unmodified conventional zeoliteframework that was used as source material. The chemical composition ofthe unmodified conventional zeolite can vary from the external surface(e.g., about the zeolite perimeter) to the inner core. However, thechemical composition of unmodified conventional zeolite framework,whether consistent or variable from the perimeter to the inner core ofthe zeolite, can be unchanged when the mesopores are formed in thezeolite. Thus, in various embodiments, forming mesopores to create thefully crystalline mesostructured zeolite does not chemically alter theframework of the conventional zeolite. The zeolite stoichiometry canalso be unchanged from the unmodified conventional fully crystallinezeolite to the fully crystalline mesostructured zeolite.

Previous attempts by others to form mesostructures in zeolites haveresulted in a change in the chemical composition of the framework of theunmodified conventional zeolite. For example, in zeolites containing Siand Al, prior methods treat the zeolite with a base selected to removemore Al than Si from the zeolite. Where such dealumination methods areemployed, at least a portion of the chemical composition in theframework of the zeolite changes, specifically, the tetracoordinatedalumina ratio changes. In various embodiments described herein, whenemploying an initial zeolite containing Si and Al, the alumina withinthe resulting mesostructured zeolite framework can remaintetracoordinated.

Direct evidence for the hybrid single-phase nature of mesostructuredzeolites was obtained via transmission electronic microscopy (“TEM”).FIGS. 10a and 10b show two details of the H—Y[MCM-41] mesostructuredzeolite microstructure at different foci in which both the crystallinityand ordered mesoporosity can be observed in a single phase. AdditionalTEM images of mesostructured zeolites are depicted in FIGS. 11-12.

Additional evidence of the hybrid nature of mesostructured zeolitescomes from catalysis. In various embodiments, the thickness of the porewall (i.e., the interior wall between adjacent mesopores) can be a valuewithin the range of from about 1 nm to about 50 nm (e.g., ˜2 nm). Inaddition to other properties, the pore wall thickness makes themesostructures having long-range crystallinity suitable for catalysis.Their characteristic, in addition to the presence of mesopores and highsurface area, appears to allow access to bulkier molecules and reduceintracrystalline diffusion resistance in the long-range crystallinemesostructured zeolites as compared to conventional unmodifiedlong-range crystalline zeolites. Enhanced catalytic activity for bulkymolecules is observed in mesostructured zeolites compared toconventional zeolites. For example, semicrystalline mesoporousmaterials, such as nanocrystalline aluminosilicate PNAs andAl-MSU-S(MFI), show significantly lower activity for cumene cracking(which is usually correlated to strong Bronsted acidity) thanconventional H-ZSM-5. Mesostructured zeolites, however, show evengreater activity than zeolites, most likely due to their fully zeoliticstructure and the presence of mesopores. For example, H-ZSM-5[MCM-41]converts 98% of cumene at 300° C., whereas commercial H-ZSM-5 converts95% in similar conditions.

In various embodiments, the treated inorganic material prepared asdescribed above can be modified according to one or more of thefollowing methods, which can be used alone or in combination. Forexample, at least a portion of the exterior surface (i.e., the geometricsurface of the inorganic material) and/or at least a portion of themesopore surfaces of the mesostructured material (e.g., a fullycrystalline mesostructured zeolite) can be modified. Similarly, thesurfaces of a crystalline nanostructure, including the external surfaceof one or more nanostructure members, the surface of one or more poresdefined within the members, and/or voids defined between adjacentmembers, can be modified.

Specifically, the mesostructured material (e.g., a fully crystallinemesostructured zeolite) can accommodate small, medium, and/or largebulky molecules on its surfaces (e.g., the mesoporous surfaces and/orthe exterior surface). In various embodiments, the ion exchangeproperties of the mesostructured materials can be used to introducechemical species. Much of the surface area that is available andaccordingly modified is the surface area of the mesoporous surfaces. Theavailable mesopore surface area in the mesostructured material iscontrolled, at least in part, by the controlled pore volume. As such,the mesostructured material can be functionalized with a wide variety ofchemical groups by various techniques.

In one or more embodiments, various metal alkoxides containing variouschemical functionalities can be reacted and grafted to the surface of amesostructured material (e.g., a fully crystalline mesostructuredzeolite) by hydrolysis of the alkoxy groups. In one or more embodiments,a metal trialkoxide (R-M(OR′)₃) can be grafted to the surface of themesostructured material. For example, trialkoxydes (R-M(OR′)₃) where Ris, for example, an amine, a phosphine, a carboxylic acid, an alcohol,or a thiol; where M is Si, Al, Ti, Sn, or Zn; and where R′ is methyl,ethyl, propyl, ethyl, or butyl, are reacted by hydrolysis of the alkoxygroup to the surface of the mesostructured material.

These surface-modified mesostructured materials can be prepared byinitially degasifying the mesostructured material, which can be inacidic form, under vacuum at a temperature from about 150 to about 550°C. for a time from about 2 to about 24 hours. Alternatively, the samplecan be degasified in an inert atmosphere, or it can be air dried attemperatures from about 150 to about 550° C. for a time from about 2 toabout 24 hours. The degasified mesostructured material can then besuspended in a dispersing medium. Suitable dispersing mediums caninclude organic solvents such as, for example, hexane, toluene, xylene,benzene, or any combination of these. Suitable metal alkoxides include,for example, silicon, aluminum, gallium, germanium, zinc, iron, tin, ortitanium alkoxides or any combination of these metal alkoxides. Themetal alkoxides can include functional groups such as, for example,amines, phosphines, carboxylic acids, hydroxides, thiols, or anycombination of these functional groups. A metal alkoxide and/or afunctional group can be dissolved in the dispersing medium prior to orafter the degasified mesostructured material is suspended in thedispersing medium. The resulting medium can be held at temperaturesranging from about room temperature to about 200° C. Refluxingconditions may also be employed. The sample can be stirred and can beheld at the determined temperature for a time period in the range offrom about 1 hour to about 1 week. Thereafter, the modifiedmesostructured material can be filtered, washed (e.g., with the chemicalused as a dispersing medium), and dried. The sample can be dried attemperatures ranging from about 20 to about 120° C. and at atmosphericpressure, under inert gas, or under vacuum. The sample can be dried fora time period ranging from about 1 hour to about 1 week. This treatmentcan be repeated or cycled from, for example, 1 time to about 10 times.In accordance with this treatment, metal alkoxides containing variouschemical functionalities can be loaded onto the mesoporous surfaceand/or the exterior surface of the mesostructured material.

In an exemplary synthesis, 1 gram of fully crystalline mesostructuredzeolite H—Y[MCM-41] was degasified under vacuum at 250° C. and wassuspended in a 50-mL toluene solution containing 1.5 grams of3-aminopropyl trimethoxysilane under an argon atmosphere. The suspensionwas stirred for 12 hours under reflux conditions. Thereafter, the solidwas filtered, washed with toluene, and dried at room temperature for 12hours. Alkylamine grafting was confirmed by infrared spectroscopy.

In other various embodiments, charged chemical species can be introducedto the mesostructured material (e.g., a fully crystalline mesostructuredzeolite) by simple ion exchange. Suitable chemical species that can beincorporated by ion exchange include, for example, metal cations,ammonium ions, phosphinium ions, quaternary amines, quaternaryphosphines, choline derived compounds, amino acids, metal complexes, orcombinations of two or more thereof.

In preparing such materials, a mesostructured material can be suspendedin an aqueous solution of a salt of the cation this is to be exchangedby ion exchange. Suitable salts include, for example, sulfates,nitrates, chlorides, or any combination thereof. Suitable cationsinclude, for example, metals, cations of the elements, quaternaryammonium compounds, choline derived compounds, and quaternaryphosphonium compounds. The ion and mesostructured material mixture canbe stirred for a time ranging from about 1 hour to about 1 week at atemperature ranging from room temperature to about 200° C. Refluxingconditions may also be employed. The sample can then be filtered, washedwith water, and dried. The drying temperatures may range from about 20to about 120° C. at, for example, atmospheric pressure, under inert gas,or under vacuum. The drying time can range from about 1 hour to about 1week. This treatment can be repeated or cycled from, for example, 1 timeto about 10 times. In accordance with this treatment, suitably sizedcharged chemical species can be loaded onto the mesoporous surfaceand/or the exterior surface of the mesostructured material. Also inaccordance with this treatment, smaller sized charged chemical speciescan be disposed in the microporous walls.

In an exemplary synthesis, 1 gram of a fully crystalline mesostructuredzeolite NH₄—Y[MCM-41] was stirred in 100 mL of a 0.01 M Pt(NH₃)₄(NO₃)₂aqueous solution for 12 hours at 70° C. The solid was then filtered,washed with deionized water, and dried at 40° C. for 12 hours. Thisprocess was repeated three times. Approximately, 1.5 weight percentPt(NH₃)₄ ²′ was added to the fully crystalline mesostructured zeolite bythis ion exchange method.

In other various embodiments, the mesostructured materials (e.g., afully crystalline mesostructured zeolite) can be neutralized.Specifically, the acidic properties of the mesostructured materials canbe used to introduce various chemical species by reaction of the acidsites of the solids with bases containing chemical functionalities ofinterest. In accordance with this modification of an external surface ofthe mesostructured material, the mesostructured material can be exposedto a base containing the desired chemical group and the neutralizationis simply allowed to happen. These neutralization reactions can be donein a gas, liquid, or solid phase. Also, the external surface of azeolite can be neutralized by the reaction of the acid sites located onthe external surface of the mesostructured zeolite by bulky bases,passivating agents, or poisons.

In preparing such materials, a mesostructured material can be suspendedin a dispersing medium in which a certain base is dissolved. Suitablebases include, for example, hydroxides, ammonia, amines, phosphine, orphosphine based bases, or their combinations. The mixture can be stirredfor a time period ranging from about 1 hour to about 1 week and can beheld at temperatures ranging from room temperature to about 200° C. Thesample can then be filtered, washed, and dried. The drying temperaturecan range from about 20 to about 120° C. at, for example, atmosphericpressure, under inert gas, or under vacuum. The drying time can rangefrom about 1 hour to about 1 week. This treatment can be repeated orcycled from, for example, 1 time to about 10 times. In accordance withthis treatment, various chemical species containing chemicalfunctionalities of interest can be loaded onto the mesoporous surfacesand/or the exterior surface of the mesostructured material. Smallersized chemical species can also be disposed in the microporous walls.

For example, in one exemplary neutralization reaction, 1 gram of adegasified H—Y[MCM-41] fully crystalline mesostructured zeolite wassuspended in 20 mL of hexane containing 0.4 mL of triphenylphosphine andstirred for 4 hours in an argon atmosphere. The sample was thenfiltered, washed with hexane, and dried at room temperature for about 12hours.

In other various embodiments, various chemical species can beincorporated into and/or with a mesostructured material (e.g., a fullycrystalline mesostructured zeolite) using the methods described before,(e.g., ion exchange or neutralization), and can thereafter be reacted toproduce a desired solid phase. For example, the fully crystallinemesostructured zeolite NH₄—Y[MCM-41] can be ion exchanged with aPt(NH₃)₄ ²⁺ and then heat treated in air at a certain temperature andthen in hydrogen at a lower temperature. Heat treatment includes, forexample, calcination at temperatures from about 300 to about 600° C. fora time ranging from about 1 hour to about 1 day under dry air flow andthen under hydrogen flow. The hydrogen concentration can range from 1 to100% at a temperature from about 200 to about 400° C. for a time periodin the range of from about 1 hour to about 1 day. In accordance withthis method, when Pt(NH₃)₄—Y[MCM-41] was calcined, Pt(NH₃)₄ ²⁺ ionsreduce to produce highly dispersed Pt nanoparticles on the surface ofthe mesostructured material.

In other various embodiments, the surface of a mesostructured material(e.g., a fully crystalline mesostructured zeolite) can be coated withvarious chemical compounds. For example, metal alkoxides (e.g., M(OR′)₄)can be reacted to the surface of the mesostructured material allowingthe hydrolysis and the formation of a metal oxide coating on the surfaceof the mesostructured material. This method includes the passivation ofthe mesopore surfaces of zeolites. For example, this method enables theformation of a silica coating on the surface of the solid to block theactive sites located on the mesopore surfaces of a mesostructuredzeolite. In this way, when a zeolite is employed as part of all of theinitial inorganic material, the accessibility of the sites in the porewalls can be increased, thereby keeping the shape selectivity typical ofconventional zeolites.

In preparing such materials, a mesostructured material (e.g., a fullycrystalline mesostructured zeolite), optionally in acidic form, can bedegasified under vacuum at temperatures between about 150 and 550° C.for a time between about 2 hours to about 24 hours. Alternatively, thesample can be degasified under an inert atmosphere or air dried attemperatures from about 150 to about 550° C. for a time from about 2hours to about 24 hours. The degasified mesostructured material can besuspended in an appropriate dispersing medium such as, for example,organic solvents including hexane, toluene, xylene, or benzene, or anycombination of these solvents. A metal alkoxide, for example, silicon,aluminum, tin, or titanium alkoxides, can be dissolved in the dispersingmedium prior to or after the suspension of the degasified mesostructuredmaterial. The mixture can be stirred for a time period ranging fromabout 1 hour to about 1 week and the mixture can be held at atemperature from room temperature to about 200° C. Refluxing conditionscan also be employed. The sample then be filtered, washed with, forexample, the chemical used as a dispersing medium, and dried. The dryingtemperatures can range from about 20 to about 120° C. at, for example,atmospheric pressure, under inert gas, or under vacuum. The drying timecan range from about 1 hour to about 1 week. This treatment can berepeated or cycled from, for example, 1 time to about 10 times.

In other various embodiments, various solid phases, for example, metals,sulfides, oxides, or combinations of these, can be loaded on the surfaceof the mesostructured material (e.g., a fully crystalline mesostructuredzeolite). Various solid phases can be incorporated on the surface ofmesostructured material by, for example, impregnation and, if needed,further thermal or chemical treatment. For example, an aqueous nickelacetate solution can be added to a fully crystalline mesostructuredzeolite until incipient wetness of the solid. The drying of the solutioncan be performed slowly, and the resulting solid can be thermallytreated. This procedure can yield nickel oxide nanoparticles on thesurface of the mesostructured material. Other solid phases that cansimilarly be loaded by impregnation onto the mesostructured materialinclude sulfide nanoparticles, molybdenum oxide, sulfide, or any othersuitable solids known or hereafter discovered in the art.

In preparing such materials, the mesostructured material (e.g., a fullycrystalline mesostructured zeolite) can be degasified in vacuum attemperatures from about 150 to about 550° C. for a time period rangingfrom about 2 hours to about 24 hours. Alternatively, the sample can bedegasified under inert atmosphere or dried air at temperatures fromabout 150 to about 550° C. for a time period in the range of from about2 hours to about 24 hours. An aqueous solution of the chemical that isto be loaded can be added to the mesostructured material. The contactbetween the solid and the solution can be maintained for time periodfrom about 1 hour to about 1 week. The contact can be done under vacuum,in an inert atmosphere, or at any air pressure. The final material canbe filtered and dried. The drying temperatures can range from about 20to about 120° C. and be at, for example, atmospheric pressure, underinert gas, or under vacuum. The drying time can range from about 1 hourto about 1 week. This treatment can be repeated or cycled, for example,from 1 time to about 10 times. In accordance with this treatment,various solid phases can be loaded onto the mesoporous surfaces and/orthe exterior surface of the mesostructured material.

In an exemplary synthesis, 1 gram of a fully crystalline mesostructuredzeolite H—Y[MCM-41] was impregnated (to incipient wetness) with 0.8 mLof a an aqueous solution (0.064 mol 1⁻¹) of ammonium heptamolybdate.Thereafter, the solid was calcined at 500° C. under flowing air. Welldispersed molybdenum oxide nanoparticles were formed inside themicropores, on the surface of the mesopores, and on the exterior surfaceof the mesostructure.

In other various embodiments, physicochemical properties ofmesostructured materials (e.g., fully crystalline mesostructuredzeolites) can be controlled by chemical vapor deposition (“CVD”) ofvarious compounds including, for example, metal alkoxides, on to asurface of a mesostructured material. In such embodiments, themesostructured material can be degassed in vacuum at a temperatureranging from about 200 to about 400° C. It can then be exposed to thechemical compound deposited by CVD. The chemical compound can be, forexample, tetramethoxysilane, provided at a certain temperature. Thistechnique can also be used to introduce nanoparticles, carbon, and metaloxide coatings on to the surface of a mesostructured material.

In preparing such materials, the mesostructured material can bedegasified in vacuum at temperatures ranging from about 150 and about550° C. for a time period ranging from about 2 hours to about 24 hours.Alternatively, the sample can be degasified under inert atmosphere ordried air at temperatures ranging from about 150 to about 550° C. for atime ranging from about 2 hours to about 24 hours. Then, the sample canbe exposed to the vapors of a chemical compound such as, for example,hydrocarbons, metal complexes, metals, organometalic compounds, orcombinations thereof at a temperature and pressure selected to stabilizethe vapor phase. This treatment can be conducted for a time period inthe range of from about 1 hour to about 1 week. The time period selecteddepends of the degree of deposition desired. The final material can bewashed and dried. The drying temperatures can range from about 20 toabout 120° C. at, for example, atmospheric pressure, under inert gas, orunder vacuum. The drying time can range from about 1 hour to about 1week. This treatment can be repeated or cycled from, for example, 1 timeto about 10 times. In accordance with this treatment, various chemicalcompounds can be loaded onto the mesoporous surfaces and/or the exteriorsurface of the material. Certain small sized vapor molecules may alsopenetrate the micropores.

In an exemplary synthesis, 1 gram of fully crystalline mesostructuredzeolite H—Y[MCM-41] was placed in a quartz reactor and heat treated in anitrogen atmosphere at 450° C. After 4 hours, the temperature wasincreased to 700° C. and then a flow of 2.0% propylene in nitrogen waspassed at 100 cc/g for 4 hours. This treatment produced a continuouscoating of pyrolitic carbon onto the surface of the fully crystallinemesostructured zeolite.

In other various embodiments, a variety of catalysts can be supported onthe surface of mesostructured materials (e.g., a fully crystallinemesostructured zeolite). In this way, homogeneous catalysts can beheterogenized. Catalysts can be supported on, for example, the mesoporesurfaces and/or on the exterior surface of the mesostructure. Suitabletechniques that dispose a catalyst on the mesostructured materialinclude direct ion exchange and chemical species used as ligands tofunctionalize a surface of the mesostructured material.

In other various embodiments, cationic homogeneous catalysts can bedirect ion exchanged with mesostructured materials (e.g., a fullycrystalline mesostructured zeolites). Cationic homogeneous catalysts canbe used to heterogenize bulky metal complexes to the surface ofmesostructured materials. In accordance with this method, cationicspecies having properties including, for example, optical properties,magnetic properties, electronic properties, bioactivity, or combinationsthereof can be heterogenized or immobilized on a surface of themesostrucutred material.

Chemical species that contain both a cationic end and a terminal endfunctional group can be ion exchanged with mesostructured materials.These terminal groups can be used as ligands for heterogenization.Accordingly, the cationic end can be direct ion exchanged with themesostructured material and the terminal end functional group can modifythe chemistry of the surface of the mesostructured material.

In preparing such materials, a mesostructured material can be suspendedin an aqueous solution of a salt of the cation that will be ionexchanged. Salts include, for example, sulfates, nitrates, chlorides, orany combinations thereof. Suitable cations include, for example, metals,cations of the elements, quaternary ammonium compounds, choline-derivedcompounds, and quaternary phosphonium compounds. Any other suitablesalts and/or cations known or hereafter discovered may also be employed.The mixture can be stirred for a time ranging from about 1 hour to about1 week and can be held at temperatures from room temperature to about200° C. Refluxing conditions may also be employed. Thereafter, thesample can be filtered, washed with water, and dried. The dryingtemperatures can range from about 20 to about 120° C. at, for example,atmospheric pressure, under inert gas, or under vacuum. The drying timecan range from about 1 hour to about 1 week. This treatment can berepeated or cycled from, for example, 1 time to about 10 times. Inaccordance with this treatment, desirable properties and/or functionalgroups can be heterogenized to the mesopore surfaces and/or the exteriorsurface of the mesostructured material.

In an exemplary synthesis, 1 gram of fully crystalline mesostructuredzeolite NH₄Y[MCM-41] was stirred in 50 mL of a 0.1 M 5,10,15,20-tetrakis(N-methyl-4-pirydyl) porphyrin pentachloride solution at roomtemperature for 12 hours. The solid was filtered and washed withdeionized water. This process was repeated three times. Finally, thesolid was dried under vacuum at 40° C. for 12 hours. As a result of thistreatment method, tetrakis (N-methyl-4-pirydyl) porphyrin pentachloridewas present on the surface of the fully crystalline mesostructuredzeolite.

In another exemplary synthesis, 1 gram of NH₄Y[MCM-41] was stirred in 50mL of a 0.1 M choline p-toluenesulfonate salt solution at roomtemperature for 12 hours. The solid was filtered and washed withdeionized water. This process was repeated three times. Finally, thesolid was dried under vacuum at 40° C. for 12 hours. As a result of thistreatment method, choline p-toluenesulfonate was present on the surfaceof the fully crystalline mesostructured zeolite.

In other various embodiments, the surface of a mesostructured material(e.g., a fully crystalline mesostructured zeolite) can first befunctionalized with a chemical species that acts as a ligand and cansubsequently be reacted with a metal complex containing ligands. Variouschemical species that can act as ligands can be incorporated on thesurface of mesostructured material. Methods for incorporating suitablechemical species that act as ligands on the surface of themesostructured material include, for example, reaction of themesostructured material with metal alkoxides, ion exchange,neutralization, and other methods selected according to the specificheterogenation application (i.e., the desired chemical species to act asa ligand on the surface of the mesostructured material). In order toheterogenize homogeneous catalysts, chemical species with selectproperties can be incorporated with ligands to form a metal complex.Suitable chemical species that may be employed as ligands in the metalcomplex include, for example, amines, phosphines, or combinationsthereof.

Following functionalization of the mesostructured material, a metalcomplex containing ligands can be exposed and allowed to bind to ligandsincorporated on the surface of the fully crystalline mesostructuredzeolite. Catalyst heterogenization occurs when at least one of theligands in the metal complex is substituted by at least one ligandattached to the surface of the mesostructured material. Alternatively,catalyst heterogenization occurs when at least one ligand attached tothe surface of the mesostructured material is substituted by at leastone of the ligands in the metal complex.

In preparing such materials, a mesostructured material containing achemical group that can be used as a ligand can be degasified undervacuum at a temperature ranging from about 150 to about 550° C.Degasification can take place over a time ranging from about 2 to about24 hours. Alternatively, the sample can be degasified under inertatmosphere or air dried at temperatures ranging from about 150 to about550° C. and for a time ranging from about 2 to about 24 hours. Theremoval of the chemical group (i.e., the ligand) should be avoided;accordingly, the degasification temperatures can range from about 60 toabout 200° C. The degasified mesostructured material can be suspended inan appropriate dispersing medium such as, for example, organic solventsincluding hexane, toluene, xylene, benzene, or any combination thereof.Homogeneous catalysts, for example, metal complexes, enzymes,supramolecular species, organic compounds, or combinations thereof, canbe dissolved in the dispersing medium prior to or after suspending thedegasified mesostructured material. The resulting mixture can be stirredfor a time ranging from about 1 hour to about 1 week at a temperatureranging from room temperature to about 200° C. Refluxing conditions mayalso be employed. The sample can then be filtered, washed with, forexample, the chemical used as dispersing medium, and dried. The dryingtemperatures can range from about 20 to about 120° C. and be at, forexample, atmospheric pressure, under inert gas, or under vacuum. Thedrying time can range from about 1 hour to about 1 week. This treatmentcan be repeated or cycled from, for example, 1 time to about 10 times.In accordance with this treatment, catalysts, for example, homogeneouscatalysts, can be attached to the mesostructure surface.

In an exemplary synthesis, 1 gram of 3-aminopropyl functionalized fullycrystalline mesostructured zeolite H—Y[MCM-41] was reacted in 150 mL ofanhydrous ethanol containing 0.1 mol of a metal complex Rh(CO)Cl(L)₂(where L is a phosphine based ligand) at room temperature for 24 hoursunder inert atmosphere. After this time, the solid was filtered, washedwith anhydrous ethanol and dried at 40° C. under vacuum. The metalcomplex Rh(CO)Cl was on the surface of the fully crystallinemesostructured zeolite.

In other various embodiments, the chemical composition framework (i.e.,the stoichiometry) of a mesostructured material (e.g., a fullycrystalline mesostructured zeolite) can be altered. Specifically, metalsatoms within the mesostructured material framework can be removed and/orsubstituted with other elements. Various techniques can be used tosubstitute some of the metal atoms of the mesostructured materialframework with other elements. For example, Al³⁺ can be replaced by Si⁴⁺by reaction with SiCl₄ in gas phase at high temperature. Other methodsto dealuminate mesostructured materials include chemical reaction withEDTA and (NH₄)₂SiF₆, typically under refluxing conditions and at highsteam temperatures.

In preparing such materials, the mesostructured material can be exposedto a medium (solid, liquid, or gas) that partially dissolves themesostructured material. Suitable mediums include, for example, steam,HF, HCl, NaOH, HNO₃, F₂, EDTA, citric acid, or oxalic acid at differentconcentrations, or any combination thereof. When the mesostructuredmaterial is an aluminosilicate (e.g., a zeolite), the medium can removeone or more of the components of the mesostructured material, such as,for example, silica and/or alumina, thereby enriching the mesostructuredmaterial framework in the component that was not removed. This treatmentcan result in a loss in crystallinity in the mesostructured material.

In an exemplary synthesis, 1 gram of H—Y[MCM-41] (Si/Al˜5) was stirredin 20 mL of a 0.25 M oxalic acid solution at room temperature for 12hours. The solid was filtered, washed with deionized water, and dried at60° C. for 12 hours. This treatment resulted in dealumination andcrystallinity loss in the mesostructured zeolite.

In various embodiments, the treated inorganic material described above(e.g., a fully crystalline mesostructured zeolite) can be combined withone or more binders and shaped as desired. Suitable binders, such asaluminum oxide, silicon oxide, amorphous aluminosilicates, clays,titania, zirconia, and others can be blended with the mesostructuredmaterial, molded, extruded, and heat treated to fabricate pellets,beads, powders (e.g., spray dried substances), layers, a monolith, orany other shapes for use in chemical processing. Binders can similarlybe blended with crystalline nanostructures and processed to fabricateshapes for use in chemical processing.

Other phases may be also added to the treated inorganic material forother purposes, such as increasing sulfur tolerance, increasing metaltolerance, increasing catalytic activity, increasing lifetime,increasing selectivity, increasing bottoms upgrading, increasinghydrothermal stability, or any combination thereof. Types of materialsemployed as other phases include, for example, alumina, silica, calciumoxide, magnesium oxide, antimony passivators, nanosized zeolites, andZSM-5 zeolite. Suitable methods and techniques for adding phases to themesostructured materials and to the crystalline nanostructured zeolitesare described herein.

In preparing such materials, a mesostructured material, asurface-modified version of a mesostructured material, a crystallinenanostructure zeolite, or a surface-modified version of a crystallinenanostructure zeolite, can be mixed with one or more binders (such as,but not limited to, clays, alumina, silica, or cellulose). Thesematerials can be mixed with the binders in any ratio and with anappropriate amount of water to form a paste that can be mixed. Themixture can be shaped by various methods such as, for example,extruding, molding, spray drying, and pelletizing. Once the solid isshaped, it can be aged by, for example, being treated in air at atemperature ranging from, for example, about 20 to about 200° C. Thesolid can be treated for a time ranging from about 1 hour to about 1week. Optionally, in order to increase the solids mechanical properties,it can be heat treated a second time at a higher temperature. The secondtemperature can vary from about 200 to about 800° C. and for a timeperiod from about 1 hour to about 1 week.

In an exemplary synthesis, 8 grams of a fully crystalline mesostructuredzeolite H—Y[MCM-41] was physically mixed with 1.5 grams of bentonite,0.3 grams of kaolin, and 0.2 g of hydroxyethyl cellulose (dry mixing).Four grams of water was added to the mixture. The resulting medium wasadditionally mixed. The paste was then extruded, aged, dried, sieved,and calcined at 450° C. for 12 hours.

Exemplary Syntheses of Fully Crystalline Mesostructured Zeolites

As discussed above, FIG. 1A is a schematic illustration of a prior artamorphous mesoporous material 100. As shown in FIG. 1A, zeolite nucleii105 a, 105 b, 105 c were aggregated around surfactant micelles undercontrolled conditions to form a solid. Thereafter, the aggregated nuclei105 a, 105 b, 105 c were washed in water and dried, and the surfactantwas extracted to provide a desired mesopore-sized pore volume 110. Eachof the zeolite nuclei, for example, 105 a, 105 b, 105 c, is a nanosizedcrystal. When they are aggregated, the material 100 is polycrystallinebecause the nuclei material lacks the long-range regular latticestructure of the crystalline state (i.e., the aggregated nuclei are notfully crystalline or truly crystalline). In contrast with FIG. 1A, FIG.1B is a schematic illustration of a fully crystalline mesostructuredzeolite 200, which features a fully crystalline zeolite structure 205with mesopores 210 penetrating throughout the volume of the zeolitestructure 205. The mesostructure 215 that surrounds the mesopores 210 isfully crystalline. The pore wall or interior wall between adjacentmesopores has a wall thickness 230. As illustrated in FIG. 1B, themesostructure 215 and the mesopores 210 are viewed from a side 220 ofthe zeolite structure 205. Although not depicted in this schematicillustration, the mesostructure and the mesopores can be viewed fromother sides of the mesostructured zeolite 200.

Referring still to FIGS. 1A and 1B, unlike the fully crystallinemesostructure 215 of the fully crystalline mesostructured zeolite 200depicted in FIG. 1B, in the aggregated crystalline mesoporous zeolitenuclei material 100, the pore walls that surround the mesopore-sizedpore volume 110 are discontinuous, featuring multiple zeolite nucleicrystals (e.g., 105 a, 105 b, 105 c).

As discussed above, the synthesis of fully crystalline mesostructuredzeolites is applicable to a wide variety of materials. One strategy isbased on the short-range reorganization of a zeolite structure in thepresence of a surfactant to accommodate mesoporosity without loss ofzeolitic full crystallinity. A zeolite is added to a pH controlledsolution containing a surfactant. Alternatively, a zeolite is added to apH controlled solution and thereafter a surfactant is added. The pHcontrolled solution can be, for example, a basic solution with a pHranging from about 8 to about 12, or from about 9 to about 11, or, thebasic solution pH can be about 10. The strength of the base and theconcentration of the basic solution are selected to provide a pH withinthe desired range. Any suitable base can be employed that falls withinthe desired pH range.

As described above, suitable surfactants that can be employed includecationic, anionic, neutral surfactants, or combinations thereof. Thequantity of surfactant is varied according to, for example, thesurfactant and the zeolite that are mixed. For example, in oneembodiment, the weight of surfactant is about equal to the weight ofzeolite added to the solution. Alternatively, the weight of surfactantcan be about half of the weight of zeolite added to the solution.

The resulting mixture can be hydrothermally treated for a period of timethat is selected to allow the fully crystalline zeolite to achieve adesired mesostructure. For example, an H—Y[MCM-41] is a fullycrystalline acidic form of faujasite having a fully crystallinemesostructure surrounding a hexagonal pore arrangement. Similarly, anH—Y[MCM-48] is a fully crystalline acidic form of faujasite having afully crystalline mesostructure surrounding a cubic pore arrangement,and an H—Y[MCM-50] is a fully crystalline acidic form of faujasitehaving a having a fully crystalline mesostructure surrounding a lamellarpore arrangement. Generally, the time and temperature are related suchthat a higher temperature requires a shorter period of time to achieve adesired mesoporosity and a certain mesostructure as compared to a lowertemperature, which would require a relatively longer period of time toachieve the same mesoporosity. Because time and temperature are related,any suitable combination of time and temperature may be employed whenhydrothermally treating the mixture. For example, the temperature rangesfrom about room temperature to about 60° C.; alternatively, thetemperature ranges from 100 to about 200° C. Where the temperature isabout 60° C. or greater, the controlled temperature conditions can takeplace under hydrothermal conditions, for example, in a sealed reactor.The time ranges from about one hour to about two weeks.

In two synthesis experiments, the parameters of time, temperature,zeolite type and quantity, and surfactant type and quantity are keptconstant; however, the pH in the first synthesis is 9 and the pH in thesecond synthesis is 11. As a result of the different pH values in thetwo synthesis experiments, the two fully crystalline zeolitemesostructures differ from one another. Specifically, the fullycrystalline zeolite mesostructure synthesized with the 9 pH solutionfeatures fewer mesopore surfaces, because fewer mesopores wereincorporated into the conventional fully crystalline zeolite, comparedto the fully crystalline zeolite mesostructure synthesized with the 11pH, which has more mesopore surfaces. Through not wishing to be bound bytheory, it is believed that the higher base concentration resulted inincreased mesoporosity.

In another exemplary synthesis, a zeolite is added to a diluted NH₄OHsolution containing cetyltrimethylammonium bromide (“CTAB”) surfactant.The mixture is hydrothermally treated at about 100 to about 200° C.,about 120 to about 180° C., about 140 to about 160° C., or about 150°C., for about 20 hours or overnight, during which the zeolite structureundergoes short-range rearrangements to accommodate the MCM-41 type ofmesostructure. Higher surfactant concentrations and longer hydrothermaltreatments would produce mesostructured zeolites with the MCM-48 type ofmesostructure. After washing and drying, the surfactant is removed by,for example, calcination or surfactant extraction. In one embodiment,the resulting material is calcined in N₂ at a maximum temperature fromabout 500 to 600° C., or at about 550° C., and then in air forsurfactant removal. The surfactant removal technique is selected based,for example, on the time needed to remove all of the surfactant from themesostructured zeolites. This synthetic scheme could be used to producemesostructured zeolites with various zeolitic structures.

Without being bound to any one theory, it is believed that thecontrolled pH solution softens the conventional fully crystallinezeolite surface enabling the surfactant to penetrate the zeolitecreating the mesostructured zeolite. More specifically, the pHconditions that are employed enable the surfactant to penetrate thestructure of the zeolite; however, it is not believed that the pHconditions dissolve the zeolite. As the surfactant penetrates thezeolite thereby forming mesopores, the penetrated portion is exposed tothe controlled pH solution and is softened, enabling further penetrationby the surfactant. The penetration continues in this fashion throughoutthe volume of the zeolite. The penetration through the zeolite volumemay be in any single direction or in a combination of directions. Forexample, the penetration may be through the x direction, the ydirection, the z direction, or any combination thereof. The penetrationdirection or rate is not necessarily linear. Penetration may be orderedor, optionally, the penetration and consequently the mesopores may bedisordered or random. Optionally, one or more of the mesoporesintersect, interconnect, converge, and/or align, which impacts thearrangement of the resulting mesoporous fully crystalline mesostructure.The surfactant enables penetration into the fully crystalline zeolite,creating mesopores. The type of surfactant determines, at least in part,the size of the mesopore including, for example, the size of themesopore diameter and/or the size of the mesopore cross section.Penetration into the conventional fully crystalline zeolite is notobserved where a controlled pH solution, for example, a base having a pHof 10 held at controlled time and temperature conditions, is mixed witha zeolite without a surfactant.

As mentioned above, certain conventional fully crystalline zeolites arevery stable (e.g., ZSM-5, MOR, CHA etc.), and it is difficult toincorporate mesoporosity into these zeolites. In such cases, strongbasic solutions having, for example, a pH ranging from about 11 to about14, or from about 12 to about 13, or an acidic solution, having, forexample, a pH ranging from about 2 to about 6, or from about 3 to about5, or at about 4, may be desired to dissolve silica and soften theconventional fully crystalline zeolite surface to enable the surfactantto penetrate and create mesopores through the fully crystalline zeolite.

Conventional fully crystalline zeolites with a dense structure (e.g.ZSM-5) are more resistant to acids and bases relative to fullycrystalline zeolites with less dense structures. Zeolites with a lowsolubility (e.g., ZSM-5) and/or a dense structure are relatively stablewith respect to penetration by acids and bases; accordingly, a dilutedtetramethyl ammonium hydroxide (“TMA-OH”) having a pH ranging from about10 to about 14 or a solution of acid, for example hydrofluoric acid,having a pH ranging from about 2 to about 6 can be used instead of adilute NH₄OH solution, having a pH ranging from about 9 to about 10, inthe synthesis scheme. More specifically, base treatment alone, even atvery high pH, might not be sufficient to soften some of the very stablezeolites. The acid HF dissolves silica and softens the structure of thedensely structured conventional fully crystalline zeolite (e.g., ZSM-5).After softening the conventional fully crystalline zeolite by exposingit to HF, the pH can be increased by including a base solution having apH from about 9 to about 11, and a suitable surfactant is added in aquantity selected according to, for example, the quantity of zeolite andthe desired mesosporosity volume. The mixture can be treated underappropriate time and temperature conditions to provide the desiredmesoporosity and resulting mesostructure in a fully crystallinemesostructured zeolite.

In another exemplary synthesis, a fully crystalline zeolite is added toan acid solution having a pH from about −2 to about 2, or from about −1to about 1, or about 0, containing a neutral surfactant, for example,PLURONIC® (available from BASF, Florham Park, N.J.). The mixture isexposed to appropriate temperature conditions for a period of timeselected to achieve a desired mesostructure. The mixture can be held atroom temperature and stirred for from about 1 day to about 1 week.Alternatively, the mixture is hydrothermally treated. In one embodiment,the mixture is hydrothermally treated at about 120° C. for from about 4hours to about 1 week. The resulting mesopores having a pore diametermeasuring from about 5 to 60 nm. A mesopore surface surrounds eachmesopore of the mesostructure.

As described above, the mesopore size and architecture may also beconveniently tuned, such as by the use of surfactants with differentaliphatic chain lengths, non-ionic surfactants, triblock copolymers,swelling agents, etc. For example, use of a surfactant with a longerchain length increases pore size; conversely, use of a surfactant with ashorter chain length results in smaller pore sizes. Additionally, theuse of a swelling agent can expand the surfactant micelles, resulting inlarger pore sizes. Any of these mesopore size and mesostructurearchitecture altering techniques may be used alone or in combination.Also, post-synthesis treatments (e.g., silanation, grafting, surfacefunctionalization, ion-exchange, immobilization of homogeneous catalystsand deposition of metal nanoclusters) can be employed to further improvethe textural properties of the materials and/or modify their surfacechemistry.

Another aspect features mesostructures such as illustrated in FIG. 1C.Such mesostructures can be achieved based on the dissolution of azeolite in a pH controlled medium, either in an acidic or basic medium,followed by hydrothermal treatment in the presence of a surfactant.Suitable surfactants that may be employed include cationic, anionic,neutral surfactants, and/or combinations thereof. The quantity ofsurfactant is varied according to, for example, the selected surfactantand the selected zeolite. For example, the weight of surfactant can beabout equal to the weight of zeolite added to the solution;alternatively, the weight of surfactant can be about half of the weightof zeolite ad that dissolves the zeolite ranges from about 10 to about14. Where the pH controlled medium is acidic, the pH ranges from about−2 to about 2; when using HF, the pH range is from about 2 to about 6.Under these more extreme pH conditions, a mesoporous solid can beobtained where the pore walls are initially amorphous. The pore wallscan later be transformed to a zeolitic phase, with or without affectingthe mesoporous structure. More specifically, after the zeolite isexposed to this aggressive pH treatment, the pH can be adjusted to about10 by adding, for example, NH₄OH and surfactant (e.g., CTAB) to produceself-assembling partially dissolved zeolites. This synthesis mixture canbe hydrothermally treated or stirred at room temperature over a periodof time to obtain a highly stable mesoporous amorphous aluminosilicate.More specifically, if the synthesis mixture is hydrothermally treatedat, for example, from about 100 to about 150° C., a highly stablemesoporous amorphous aluminosilicate can be obtained. Alternatively, thesynthesis mixture can be stirred at room temperature for sufficient time(from about 4 hours to about 1 day) to obtain a highly stable mesoporousamorphous aluminosilicate. The mesoporous amorphous aluminosilicatemaintains its mesoporosity after boiling for 48 hours under refluxconditions. The acidity of the material produced is higher than that ofamorphous mesoporous materials obtained from non-zeolitic silica andalumina sources. Where the synthesis mixture is hydrothermally treatedfor a longer period of time (from about 12 hours to about 2 weeks) azeolitic mesostructure is obtained. By adjusting the synthesisconditions (e.g., pH, time, temperature, zeolite type, surfactantconcentration) different zeolite nanostructures (e.g., nanotubes,nanorings, nanorods, nanowires, nanoslabs, nanofibers, nanodiscs, etc.)can be produced. Referring again to FIG. 1C, a nanostructure including,for example, nanorods is made from adjacent members (e.g., a firstnanorod adjacent a second nanorod). Voids can be formed between adjacentmembers (e.g., adjacent nanorods). Each nanostructure member defines aplurality of pores (e.g., each nanorod has pores in its structure).Different members can join together within a single nanostructure, forexample, a nanorod may be adjacent a nanoring.

Zeolitic nanorods (“ZNRs”) have been prepared by this approach in threesteps: (i) basic treatment of a zeolite in a pH controlled medium topartially dissolve the zeolite and produce a suspension of amorphousaluminosilicate, (ii) pH adjustment and surfactant addition to produceMCM-41, and (iii) hydrothermal treatment of the resulting solid at atemperature typically ranging from about 100 to about 200° C. for fromabout 12 hours to about 2 weeks. During the last step, the MCM-41 (thehexagonal pore arrangement) mesostructure is first transformed to MCM-48(the cubic pore arrangement) and is then transformed to MCM-50 (thelamellar pore arrangement), while the amorphous pore walls aretransformed to a crystalline zeolitic phase. MCM-50 is a lamellarstructure and is a precursor to zeolitic nanostructures including, forexample, nanotubes, nanorings, nanorods, nanowires, nanoslabs, etc. Thespecific nanostructure formed by using steps (i)-(iii) is determined bythe selected zeolite, surfactant, temperature, time, and pH. The zeoliteand other conditions can be selected to achieve a single nanostructureshape (e.g., all nanorod) or, alternatively, multiple nanostructureshapes. Without being bound to any single theory, it appears thatnanostructures are achieved, at least in part, because the zeolitedissolved by a pH controlled solution into a suspension of amorphousaluminosilicate retains some degree of the zeolitic connectivity that ischaracteristic of a zeolite starting material. It is expected that someof the IR spectra bands characteristic of zeolites remain present in thedissolved solution (i.e., in the suspension of amorphousaluminosilicate). In contrast, if, rather than dissolving a zeolite toproduce a suspension of amorphous aluminosilicate, an alumina, aslilica, or an amorphous aluminosilicate were exposed to steps(ii)-(iii), described above, the nanostructure fails to form. Thebuilding blocks of connectivity present in dissolved zeolite solutionappear to play a part in forming nanostructures.

Although the nanostructures are crystalline they are not fullycrystalline. They have a few units in one direction and are semicrystalline or are polycrystalline. Semi crystalline and polycrystallinerefer to, for example, nanosized crystals, crystal nuclei, orcrystallites that, for example, aggregate to form a solid. Unit cellsare the simplest repeating unit in a crystalline structure orcrystalline material. Nanostructures have an open structure. They have ahigh surface area due to an extended structure in the space as well asdue to spaces between multiple structures or voids within the structuresthemselves. Generally, these nanostructures also have a high externalsurface area. In one embodiment, one nanostructure is adjacent anothernanostructure. FIG. 1C depicts a TEM image of a nanosostructured zeolitewhere the nanostructure shape includes nanorods. The nanorods have athickness measuring about 5 nm. As depicted, the nanorods sit adjacentone another and the nanorods curve. The background of the curved rodsseen in the TEM image is noise and it should be ignored.

Applications

The unique structure of mesostructured zeolites will be useful to avariety of fields, and should address certain limitations associatedwith conventional zeolites. As catalysis is an important field ofapplication for zeolites, special emphasis is placed on the catalyticapplications of mesostructured zeolites.

The combination of a mesostructure, a high surface-area, and controlledpore or interior thickness as measured between adjacent mesopores shouldprovide for access to bulky molecules and reduce the intracrystallinediffusion barriers. Thus, enhanced catalytic activity for bulkymolecules should be observed over mesostructured zeolites, as comparedto conventional zeolites. See FIGS. 13-14. The subject matter of FIGS.13-20 a involves reactions with 1,3,5-triisopropylbenzene beingcatalytically cracked to form 1,3-diisopropyl benzene. The1,3,5-triisopropylbenzene is representative of molecules present incrude oil and 1,3-diisopropyl benzene is representative of a productwithin the gasoline range. These experiments are a surrogate formolecules present in crude oil that are cracked to form gasoline.

FIG. 13 depicts the process of catalytic cracking of 1,3,5-triisopropylbenzene by zeolite H—Y. Catalytic cracking is selectivity and/orefficiency limited, because diffusion is limited by the small pore sizeof the zeolite H—Y. Because the conventional unconverted zeolite crystalhas limited diffusion, it is difficult for the initial reaction product(e.g., 1,3-diisopropyl benzene) to exit the zeolite. As a result, overcracking occurs and light compounds are formed resulting in excessformation of undesirable products, such as cumene, benzene, and coke.FIG. 14 depicts the process of catalytic cracking of 1,3,5-triisopropylbenzene by a mesostructured zeolite. In contrast to catalytic crackingwith the unmodified conventional zeolite H—Y, the larger pore size, thecontrolled mesopore volume, and the controlled interior or pore wallthickness present in the fully crystalline mesostructured zeolitefacilitates the exit of desired products (i.e., 1,3-diisopropyl benzene)from the mesostructure, and over cracking that produces cumene, benzene,and coke is avoided. As a result, there is a higher conversion of thedesired product, 1,3-diisopropyl benzene.

Acid catalysts with well-defined ultra-large pores are highly desirablefor many applications, especially for catalytic cracking of the gas oilfraction of petroleum, whereby slight improvements in catalytic activityor selectivity would translate to significant economic benefits. As atest reaction, we have examined the catalytic cracking of1,3,5-triisopropylbenzene (critical dimension 0.95 nm) to produce1,3-diisopropyl benzene. FIG. 15 depicts catalytic activity for1,3,5-triisopropyl benzene cracking shown as percent conversion to1,3-diisopropyl benzene vs. time for the mesostructured zeoliteH—Y[MCM-41], which is labeled Meso-HY, the zeolite H—Y, and aconventional Al-MCM-41. Catalytic cracking was performed when 50 mL/minof He saturated with 1,3,5-triisopropylbenzene at 120° C. was flowed at200° C. over 50 mg of each catalyst. The H—Y[MCM-41] mesostructuredzeolite demonstrated superior catalytic activity for this crackingreaction after 400 minutes at 200° C. (93% conversion) compared to theH—Y zeolite (71% conversion) and the mesoporous Al-MCM-41 (39%conversion) (see FIG. 15). This result was attributed to its combinationof strong acidity and mesostructured nature. The mesopores and themesostructure surrounding the mesopores greatly facilitated thehydrocarbon diffusion within the H—Y[MCM-41] catalyst thereby improvingconversion. The H—Y[MCM-41] mesostructured zeolite is stable andmaintains mesostructure integrity even under harsh conditions. FIG. 17depicts the hydrothermal stability of H—Y[MCM-41], labeled Meso-HY,compared to the non-mesolytic zeolite Al-MCM-41. For example, the boiledmesostructured zeolite H—Y[MCM-41], labeled Meso-HY, also maintained itsphysicochemical integrity even after being boiled for several days,exhibiting a high 1,3,5-triisopropylbenzene activity (87% conversion to1,3-diisopropyl benzene after 400 minutes) even after such severetreatment. The term boiled is used for convenience; however, thespecific treatment to the material includes suspending the solid inwater and heating the water and solid material under reflux conditions.See FIG. 17. This outcome illustrates the superior hydrothermalstability of H—Y[MCM-41] over the amorphous Al-MCM-41 catalyst, whichlost its activity and ordered mesostructure after exposure to similarconditions. These results show that hydrothermally stable H—Y[MCM-41] isa crystalline material and its crystallinity contrasts the amorphousAl-MCM-41 catalyst that structurally collapsed after boiling, renderingit unable to convert appreciable quantities via catalytic cracking.

FIG. 19 depicts catalytic activity for 1,3,5-triisopropyl benzenecracking shown as percent conversion vs. time for H-ZSM-5[MCM-41],labeled Meso-H-ZSM-5, and its zeolitic version, H-ZSM-5. A 50 mL/min Heflow saturated with 1,3,5-triisopropylbenzene at 120° C. was flowed at200° C. over 50 mg of each catalyst, H-ZSM-5[MCM-41] and H-ZSM-5.H-ZSM-5 is used as an important additive in cracking catalysts toincrease propylene production and improve octane number in gasoline.However, due to its small pores, H-ZSM-5 is inactive in1,3,5-triisopropylbenzene cracking at 200° C. (<1% conversion to1,3-diisopropyl benzene after 400 min). The incorporation of MCM-41mesostructure in this zeolite (H-ZSM-5[MCM-41]) successfully achievedsubstantial activity, with 40% conversion of 1,3,5-triisopropylbenzeneto 1,3-diisopropyl benzene after 400 min (see FIG. 19). In this case,the activity was attributed to the mesopores and strong acidity of themesostructured zeolite.

More than 135 different zeolitic structures have been reported to date,but only about a dozen of them have commercial applications, mostly thezeolites with 3-D (3-dimensional) pore structures. The incorporation of3-D mesopores may be beneficial for zeolites with 1-D and 2-D porestructures as it would greatly facilitate intracrystalline diffusion.Zeolites with 1-D and 2-D pore structures are not widely used, becausethe pore structure is less then optimal. To illustrate the potential ofmesostructure processing of zeolites with low pore interconnectivity,H-MOR with 1-D pores were prepared with an MCM-48 mesostructure byexposing the H-MOR zeolite with 1-D pores to a pH controlled solution inthe presence of a surfactant under suitable time and temperatureconditions, described above. The resulting H-MOR[MCM-48] with 3-Dmesostructured structures was examined for the catalytic cracking of1,3,5-triisopropylbenzene at 200° C. FIG. 18 depicts catalytic activityfor 1,3,5-triisopropyl benzene cracking shown as conversion to1,3-diisopropyl benzene vs. time for H-MOR[MCM-48] labeled Meso-HMOR,and its zeolitic version, H-MOR. A 50 mL/min He flow saturated with1,3,5-triisopropylbenzene at 120° C. was flowed at 200° C. over 50 mg ofeach catalyst, H-MOR[MCM-48] and H-MOR. Catalytic cracking withH-MOR[MCM-48] exhibited 50% conversion after 400 minutes, which wassignificantly higher compared to the 7% conversion achieved by H-MOR(see FIG. 18). Zeolites with 1-D pore structures show a more dramaticimprovement when exposed to the mesostructure process as compared to thezeolites with 2-D pore structures, but this is to be expected becausethe 1-D pore structure zeolites begin with provide more limiteddiffusion. When exposed to the mesostructure process, zeolites with 2-Dpore structures result in 3-D mesostructures. Exposing 1-D and 2-D porestructure zeolites to the instant process for forming mesostructures infully crystalline inorganic material may increase the usefulness ofthese otherwise underused zeolites.

Mesostructured zeolites not only showed much higher catalytic activity,but also enhanced selectivity over zeolites. Referring now to FIG. 16, acommercially available zeolite H—Y was employed to catalytically crack1,3,5-triisopropylbenzene. The resulting products were 1,3-diisopropylbenzene, benzene, and cumene and the fractional composition results werenormalized to be 100%. The mesostructured zeolite, labeled Meso-HY,which is H—Y[MCM-41], was employed to catalytically crack1,3,5-triisopropylbenzene under identical conditions employed with H—Y.Increased production of 1,3-diisopropyl benzene (about 110% of the1,3-diisopropyl benzene produced with the zeolite H—Y) and decreasedproduction of benzene and cumene (about 75% of the benzene and cumeneproduced with the zeolite H—Y) was observed. In this example,H—Y[MCM-41] mesostructured zeolite produced only 75% of the benzenegenerated by the H—Y zeolite. See FIG. 16. Benzene is a toxic compoundwhose presence in gasoline is being increasingly restricted bylegislation. The benzene production was even lower in the case ofH-MOR[MCM-48], and was minimal in the case of H-ZSM-5[MCM-41]. Thedecrease in benzene production has been observed in small zeolitecrystals, and was related to the intrinsic ability of crystals withhigher surface areas to limit successive cracking reactions. It alsoreduced the formation of coke, which is an undesired end-product of thecracking process that can be responsible for catalyst deactivation.Thus, the mesostructured zeolites not only provided for higher catalyticactivity and selectivity, but also longer catalyst life time.

Zeolitic nanorods another form of mesostructured zeolite, also enhancecatalytic activity by increasing active-site accessibility. Therod-shape ZNRs are only nanometer-sized in diameter, so internaldiffusional resistance is minimal. These new mesostructured zeolites(also referred to as nanostructures) were tested as cracking catalystsfor the gas oil fraction of petroleum to assess their potential. FIG.20a depicts, on the left-hand side Y axis, the percent conversion of1,3,5-triisopropylbenzene to 1,3-diisopropyl benzene versus time forH-MOR[ZNR] and H-MOR. The ratio of benzene produced by H-MOR-to-benzeneproduced by H-MOR[ZNR] as a function of time is also shown on thesecondary Y axis located on the right-hand side of FIG. 20a , and anarrow is present on the line that connects this data. A helium flow of50 mL/min saturated with 1,3,5-triisopropylbenzene at 120° C. wasintroduced over 50 mg of each catalyst, H-MOR[ZNR] and H-MOR, at 200° C.

In the cracking of 1,3,5-triisopropylbenzene, the conventional H-MORzeolite showed a low activity (7% conversion to 1,3-diisopropyl benzeneafter 400 min) due to its medium-sized (0.65 to 0.70 nm), 1-D pores. Incontrast, H-MOR[ZNR] achieved a much higher catalytic activity undersimilar conditions (52% conversion to 1,3-diisopropyl benzene) (see FIG.20a ). This significant increase in catalytic activity was attributed toZNRs' higher surface areas, readily accessible active sites, andimproved intracrystalline diffusivity.

Besides increased activity, ZNRs also showed improved selectivity due totheir nanostructured rod-shape morphology. For example, H-MOR[ZNR]produced 3 times less benzene per mole of 1,3,5-triisopropylbenzeneconverted as compared to the commercial zeolite H-MOR (see the secondaryY axis on the right-hand side of FIG. 20a ). Benzene may include, forexample, benzene derivatives such as, for example, toluene, xylene, andother related derivative compounds. This significant increase inselectivity also helped to reduce coke formation, which has been a majorproblem with conventional cracking catalysts, especially thosecontaining 1-D pores, such as mordenite.

The simple, inexpensive, and generalized synthesis strategies describedherein allow for the preparation of ZNR, a crystalline material withwalls that are only several nanometers thick (e.g., 3-20 nm), in whichnanorings and junctions are common. The novel synthesis strategies werebased on the “programmed” zeolitic transformation of mesoporousmaterials, which avoided the typical drawbacks of nanoscaled zeolitesynthesis (e.g., low yield, difficulty in separation, and high pressuredrops) and did not require the use of a layered precursor. The uniquecrystalline structure of ZNRs provided for improved catalytic conversionof bulky molecules by increasing the accessibility to its microporosity,while reducing interparticle and intraparticle diffusion barriers.

Referring now to FIGS. 20b and 20c , mesostructured zeolites were testedfor crude oil refining via Microactivity Test (“MAT;” ASTM D-3907). Thisis a well known and widely accepted technique to estimate theperformance of fluid catalytic cracking (“FCC”) catalysts. Vacuumgas-oil was used as feed in a fluid-bed stainless steel reactor. Theexperiments were conducted under identical conditions withmesostructured zeolites and their conventional zeolites counterparts.

FIG. 20b depicts MAT results of a conventional fully crystalline zeoliteH—Y (Si/Al˜15) and its fully crystalline mesostructured versionH—Y[MCM-41]. MAT conditions included a reaction temperature of 500° C.,a catalyst contact time of 60 seconds, a catalyst charge of 1 gram, acatalyst/vacuum gas oil ratio of 2, and a WHSV of 30 g/h/g. Theconversion (i.e., how much of the vacuum gas oil feed was converted intoproduct), with all yield normalized to 100% for comparison purposes, forthe unmodified fully crystalline zeolite H—Y was 61.22%, and for thefully crystalline mesostructured zeolite H—Y[MCM-41] was 67.20%.Although not depicted in FIG. 20b , the results of this test providedliquid petroleum gases (“LPG”) fraction of H—Y of 17.45% and LPGfraction of H—Y[MCM-41] of 15.27%.

FIG. 20c depicts the composition of the LPG fraction obtained by MAT ofa conventional fully crystalline zeolite H—Y (Si/Al˜15) and its fullycrystalline mesostructured version H—Y[MCM-41], described above inconjunction with FIG. 20b . The composition of the LPG fraction wasanalyzed to determine the components of the LPG fraction. Where thefully crystalline zeolite H—Y was used, the LPG fraction was 17.45%.Where the fully crystalline mesostructured zeolite HY[MCM-41] was used,the LPG fraction was 15.27%. In addition, the fully crystallinemesostructured zeolites produced more olefins, which are desiredproducts. Referring now to the X-axis on FIG. 20c , the label C3indicates propane, the label C3= indicates propene, the label i-C4indicates isobutane, the label n-C4 indicates normal butane, the labeli-C4= indicates isobutene, and the label n-C4= indicates normal butene.Specifically, the fully crystalline mesostructured zeolite producedincreased propene, isobutene, and normal butene in the LPG fraction ascompared to the unmodified fully crystalline zeolite. Further, the fullycrystalline mesostructured zeolite produced a lesser fraction of LPGthan with its counterpart conventional unmodified fully crystallinezeolite. The internal wall thickness of the fully crystallinemesostructured zeolite is less than the internal wall thickness of theunmodified fully crystalline zeolite. Thus the thinner internal walls inthe fully crystalline mesostructured zeolites reduced hydrogen transferreactions, which are responsible for the undesired conversion of olefinsto paraffins. Accordingly, an increased number of desired olefins areproduced where fully crystalline mesostructured zeolites are usedinstead of conventional unmodified fully crystalline zeolites.

In the MAT, generally, the samples were displayed in a fluidized-bedstainless steel reactor. Reaction temperature was 500° C., the amount ofcatalyst was 3.0 g, the catalyst/oil ratio was 2.0, the WHSV was 30g/h/g, and the contact time was 60 seconds. These tests showed thatusing H—Y[MCM-41] in place of conventional H—Y resulted in a 43%increase in gasoline production, a 75% increase in propylene and a 110%increase in butenes. Additionally, there is a 32% decrease in cokeformation, a 23% decrease in total dry gas, and a 12% decrease in LPG.The presence of mesopores in the H—Y[MCM-41], which has at least doublethe surface area of H—Y, favors the cracking of the larger moleculespresent in the crude oil, which cannot be transformed within themicropores of conventional zeolites. Typically, conventional zeoliteshave pores measuring about 0.7 nm, which are too small to efficientlyprocess desirable products, for example, alkyl benzene, contained inheavy crude oil fractions. Larger pore sizes are required to facilitateimproved surface area contact (including within the pore walls ormesopore surfaces) with the hydrocarbon materials. For comparison, thediameter of each of the mesopores, which are surrounded by the mesoporesurfaces of the fully crystalline mesostructure of the invention, canmeasure, e.g., about 2 nm. The increased production of light olefins wasrelated to the reduction of hydrogen transfer reaction due to thepresence of favorable interior or pore wall thickness in the fullycrystalline mesostructured zeolites (e.g., ˜2 nm) as opposed to thethick crystals of conventional zeolites (e.g., ˜1000 nm). This interioror pore wall thickness also results in reduction of over-cracking,significantly reduces coke formation, and reduces production of totaldry gas and LPG.

Pyrolysis of plastics has gained renewed attention due to thepossibility of converting these abundant waste products into valuablechemicals while also producing energy. Acidic catalysts, such aszeolites, have been shown to be able to reduce significantly thedecomposition temperature of plastics and to control the range ofproducts generated. However, the accessibility of the bulky moleculesproduced during plastic degradation has been severely limited by themicropores of zeolites.

The catalytic degradation of polyethylene (“PE”) by commerciallyavailable zeolites and their corresponding mesostructured zeolites wasstudied by thermal gravimetric analysis (“TGA”). FIG. 21 depicts thepercentage of polyethylene weight lost vs. temperature for the followingmixtures of catalysts in weight ratio to PE. The curves labeled (A)-(G)depict results of the following degradation curves: (A): no catalyst,(B): H-ZSM-5:PE, 1:2; (C): H-ZSM-5[MCM-41]:PE, 1:2; (D): H-ZSM-5:PE,1:1; (E) H-ZSM-5:PE, 2:1; (F): H-ZSM-5[MCM-41]:PE, 1:1; and (G)H-ZSM-5[MCM-41]:PE, 2:1. In all cases, fully crystalline mesostructuredzeolites allow for reduced decomposition temperatures compared tounmodified commercial zeolites (by ˜35° C. in the case of(C)H-ZSM-5[MCM-41] vs. (B) H-ZSM-5), even at high catalyst:PE ratios(see FIG. 21). In fact, referring to the curve labeled (F), with anH-ZSM-5[MCM-41]:PE weight ratio of 1:1, a lower decompositiontemperature was achieved compared to that required by referring to curvelabeled (E), a ZSM-5:PE weight ratio of 2:1.

With their improved accessibility and diffusivity compared toconventional zeolites, fully crystalline mesostructured zeolites mayalso be employed in place of unmodified conventional zeolites in otherapplications, such as gas and liquid-phase adsorption, separation,catalysis, catalytic cracking, catalytic hydrocracking, catalyticisomerization, catalytic hydrogenation, catalytic hydroformilation,catalytic alkylation, catalytic acylation, ion-exchange, watertreatment, pollution remediation, etc. Many of these applications suffercurrently from limitations associated with the small pores of zeolites,especially when bulky molecules are involved. Mesostructured zeolitespresent attractive benefits over zeolites in such applications.

Organic dye and pollutant removal from water is of major environmentalimportance, and represents the third major use of zeolites (accountingfor 80 tons of zeolites per year). However, most of the organic dyes arebulky, which make their removal slow or incomplete, requiring a hugeexcess of zeolites in the process. Fully crystalline mesostructuredzeolites offer significant advantage over unmodified conventionalzeolites in organic dye and pollutant removal with their larger surfacearea and pore size.

Application in Petrochemical Processing

The mesostructured materials can have one or more of controlled porevolume, controlled pore size (e.g., cross sectional area and/ordiameter), and controlled pore shape. Hydrocarbon reactions, includingpetrochemical processing, are mass-transfer limited. Accordingly, afully crystalline mesostructured catalyst with controlled pore volume,pore size, and/or pore shape can facilitate transport of the reactantsto and within active catalyst sites within the fully crystallinemesostructured catalyst and transport the products of the reaction outof the catalyst. Fully crystalline mesostructured inorganic materials,for example, zeolites, enable processing of very large or bulkymolecules, with dimensions of, for example, from about 2 to about 60 nm,from about 5 to about 50 nm, and from about 30 to about 60 nm.

Hydrocarbon and/or petrochemical feed materials that can be processedwith the mesostructured materials (e.g., fully crystallinemesostructured zeolitic materials) and/or the crystalline nanostructurematerials include, for example, a gas oil (e.g., light, medium, or heavygas oil) with or without the addition of resids. The feed material caninclude thermal oils, residual oils, (e.g., atmospheric tower bottoms(“ATB”), heavy gas oil (“HGO”), vacuum gas oil (“VGO”), and vacuum towerbottoms (“VTB”)), cycle stocks, whole top crudes, tar sand oils, shaleoils, synthetic fuels (e.g., products of Fischer-Tropsch synthesis),heavy hydrocarbon fractions derived from the destructive hydrogenationof coal, tar, pitches, asphalts, heavy and/or sour and/or metal-ladencrude oils, and waxy materials, including, but not limited to, waxesproduced by Fischer-Tropsch synthesis of hydrocarbons from synthesisgas. Hydrotreated feedstocks derived from any of the above describedfeed materials may also be processed by using the fully crystallinemesostructured zeolitic materials and/or the crystalline nanostructurematerials.

Heavy hydrocarbon fractions from crude oil contain most of the sulfur incrude oils, mainly in the form of mercaptans, sulfides, disulfides,thiophenes, benzothiophenes, dibenzothiophenes, andbenzonaphthothiophenes, many of which are large, bulky molecules.Similarly, heavy hydrocarbon fractions contain most of the nitrogen incrude oils, principally in the form of neutral N-compounds (indole,carbazole), basic N-compounds (pyridine, quinoline, acridine,phenenthridine), and weakly basic N-compounds (hydroxipyridine andhydroxiquinoline) and their substituted H—, alkyl-, phenyl- andnaphthyl-substituted derivatives, many of which are large, bulkymaterials. Sulfur and nitrogen species are removed for production ofclean fuels and resids or deeper cut gas oils with high metals contentcan also be processed using the mesostructured materials and/or thecrystalline nanostructure materials described herein.

In various embodiments, the mesostructured material and/or thecrystalline nanostructured material can be employed in chemicalprocessing operations including, for example, catalytic cracking,fluidized catalytic cracking, hydrogenation, hydrosulfurization,hydrocracking, hydroisomerization, oligomerization, alkylation, or anyof these in combination. Any of these chemical processing operations maybe employed to produce, for example, a petrochemical product by reactinga petrochemical feed material with the mesostructured material and/orthe crystalline nanostructured materials described herein.

In various embodiments, the mesostructured material and/or thecrystalline nanostructured material can be used as an additive to othercatalysts and/or other separation materials including, for example, amembrane, an adsorbent, a filter, an ion exchange column, an ionexchange membrane, or an ion exchange filter.

In various embodiments, the mesostructured material and/or thecrystalline nanostructured material can be used alone or in combinationas an additive to a catalyst. The mesostructured material and/or thecrystalline nanostructured material can be added at from about 0.05 toabout 100 weight percent to the catalyst. The additive may be employedin chemical processing operations including, for example, catalyticcracking, fluidized catalytic cracking, hydrogenation,hydrosulfurization, hydrocracking, hydroisomerization, oligomerization,alkylation, or any of these in combination. For example, the addition ofsmall amounts of fully crystalline mesostructured zeolites and/orcrystalline nanostructured zeolites to conventional commerciallyavailable FCC catalysts allows for improvement in the catalyticperformance.

Generally, FCC uses an FCC catalyst, which is typically a fine powderwith a particle size of about 10 to 200 microns. The FCC catalyst can besuspended in the feed and propelled upward into a reaction zone. Arelatively heavy hydrocarbon or petrochemical feedstock (e.g., a gasoil) can be mixed with the FCC catalyst to provide a fluidizedsuspension. The feed stock can be cracked in an elongated reactor, orriser, at elevated temperatures to provide a mixture of petrochemicalproducts that are lighter hydrocarbon products than were provided in thefeed stock. Gaseous reaction products and spent catalyst are dischargedfrom the riser into a separator where they can be regenerated. TypicalFCC conversion conditions employing FCC catalysts include a riser toptemperature of about 500 to about 595° C., a catalyst/oil weight ratioof about 3 to about 12, and a catalyst residence time of about 0.5 toabout 15 seconds. The higher activity of the mesostructured catalystsand/or the crystalline nanostructure catalyst can enable less severeprocessing conditions, such as, for example, lower temperature, lowercatalyst to oil ratios, and/or lower contact time.

In various embodiments, a small amount of mesostructured material (e.g.,fully crystalline mesostructured zeolites) and/or crystallinenanostructured material blended with conventional FCC catalysts canenable pre-cracking of the bulkier molecules by the mesostructuredmaterial and/or crystalline nanostructured material contained in theblend. Conventional FCC catalysts have pore sizes too small toaccommodate bulkier molecules. After the bulkier molecules have beenpre-cracked they are processed in the small pores of the conventionalFCC catalyst.

FIG. 23 depicts MAT yield results where a fully crystallinemesostructured zeolite H—Y[MCM-41] was employed as an additive to aconventional unmodified zeolite H—Y for fluid catalytic cracking of avacuum gas oil. The results from left to right on the x-axis show 100%H—Y with no additive, 10% H—Y[MCM-41] additive to the catalyst, 20%H—Y[MCM-41] additive to the catalyst, 50% H—Y[MCM-41] additive to thecatalyst, and 100% H—Y[MCM-41]. MAT conditions include a reactiontemperature of 500° C., catalyst contact time of 60 seconds, a catalystcharge of 1 gram, a catalyst-to-vacuum gas oil ratio of 2, and a WHSV of30 g/h/g. In FIG. 23, the bar labeled LCO shows the yield of light cycleoil and the bar labeled HCO shows the yield of fractions heavier thangasoline.

Referring still to FIG. 23, the addition of the fully crystallinemesostructured zeolite to the conventional FCC catalyst produced asignificant impact over the yield structure that does not correspond tothe linear combination of both materials. The data suggests thepre-cracking effect of a fully crystalline mesostructured zeoliteadditive to a catalyst. A significant conversion improvement in theheavier fractions (“HCO”) was obtained at 10% fully crystallinemesostructured zeolite. The incremental amounts of fully crystallinemesostructured zeolites, 20% and 50%, does not produce an increase ingasoline production or conversion, and does not decrease the HCO ascompared to the 10% additive quantity. This data supports thepre-cracking effect of the fully crystalline mesostructured zeoliteadditive. The higher amount of total dry gas, LPG, and coke producedwhen fully crystalline mesostructured zeolites as used as FCC additivesmay be due to the higher conversion obtained when the fully crystallinezeolite materials were employed. A similar pre-cracking effect can beexpected where a crystalline nanostructure zeolite is employed as anadditive.

In various embodiments, mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructurematerials can be blended with conventional catalysts. The additivemesostructured materials and/or crystalline nanostructure materials canbe incorporated into the conventional catalyst pellet. Shaped (e.g.,pelletized) mesostructured materials and/or crystalline nanostructurematerials can be mixed with the catalyst pellet. Alternatively, aconventional catalyst and the mesostructured and/or nanostructuredmaterials can be layered together. Any such mixture can be used in arefining application, for example, in fluidized catalytic crackingdirectly as is done with other additives. The amount of mesostructuredzeolite added and the manner by which it is blended can be used to tunethe yield and/or the structure of the products.

In one or more embodiments, the addition of or incorporation ofmesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials to conventionalcommercially available Thermofor Catalytic Cracking (“TCC”) catalystsprovides an improvement in the catalytic performance. The TCC process isa moving bed process that uses pellet or bead shaped conventionalcatalysts having an average particle size of about one-sixty-fourth toone-fourth inch. Hot catalyst beads progress with a hydrocarbon orpetrochemical feed stock downwardly through a cracking reaction zone.The hydrocarbon products are separated from the spent catalyst andrecovered. The catalyst is recovered at the lower end of the zone andrecycled (e.g., regenerated). Typically, TCC conversion conditionsinclude an average reactor temperature from about 450 to about 510° C.,a catalyst/oil volume ratio of from about 2 to about 7, and a reactorspace velocity of from about 1 to about 2.5 vol/hr/vol. Mesostructuredmaterials and/or crystalline nanostructured materials can be substitutedfor TCC catalysts to improve the catalytic cracking of petrochemical orhydrocarbon feed stocks to petroleum product. Alternatively, themesostructured materials and/or crystalline nanostructured materials canbe blended with the TCC catalyst.

In various embodiments, mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructuredmaterials can be used as catalyst additives in any other catalyticapplication. For example, they may be used as additives in processeswhere bulky molecules must be processed.

In other various embodiments, mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructuredmaterials can be used in hydrogenation. Conventional zeolites are goodhydrogenation supports because they possess a level of acidity neededboth for the hydrogenation of the aromatic compounds and for toleranceto poisons such as, for example, sulfur. However, the small pore size ofconventional zeolites limit the size of the molecules that can behydrogenated. Various metals, such as Pt, Pd, Ni, Co, Mo, or mixtures ofsuch metals, can be supported on mesostructured materials using surfacemodification methods, for example, ion exchange, described herein. Thehydrogenation catalytic activity of mesostructured materials modified tosupport various metals (e.g., doped with metals) shows a higherhydrogenation activity for bulky aromatic compounds as compared to otherconventional materials, for example, metal supported on alumina, silica,metal oxides, MCM-41, and conventional zeolites. The mesostructuredmaterials modified to support various metals also show, compared toconventional materials, a higher tolerance to sulfur, for example,sulfur added as thiophene and dibenzothiophene, which are common bulkycomponents of crude oil that often end up in gas oil fractions.

In other various embodiments, mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructuredmaterials can be used in hydrodesulfurization (“HDS”), including, forexample, deep HDS, hydrodesulfurization of 4,6-dialkyldibenzothiophenes.Deep removal of sulfur species from gas oil has two main limitations: i)the very low reactivity of some sulfur species, for example,dimethyldibenzothiophenes and ii) the presence of inhibitors in the feedstocks such as, for example, H₂S. Deep HDS is currently done with activemetal sulfides on alumina, silica/alumina, and alumina/zeolite.

Generally, during HDS the feed stock is reacted with hydrogen in thepresence of an HDS catalyst. Oxygen and any sulfur and nitrogen presentin the feed is reduced to low levels. Aromatics and olefins are alsoreduced. The HDS reaction conditions are selected to minimize crackingreactions, which reduce the yield of the most desulfided fuel product.Hydrotreating conditions typically include a reaction temperature fromabout 400 to about 900° F., a pressure between 500 to 5,000 psig, a feedrate (LHSV) of 0.5 hr⁻¹ to 20 hr⁻¹ (v/v), and overall hydrogenconsumption of 300 to 2,000 scf per barrel of liquid hydrocarbon feed(53.4-356 m³ H₂/m³ feed).

Suitable active metal sulfides include, for example, Ni and Co/Mosulfides. Zeolites provide strong acidity, which improves HDS ofrefractory sulfur species through methyl group migration. Zeolites alsoenhance the hydrogenation of neighboring aromatic rings. Zeolite acidityenhances the liberation of H₂₅ from the metal sulfide increasing thetolerance of the catalyst to inhibitors. However, bulky methylatedpolyaromatic sulfur species are not able to access the acidic sites ofconventional zeolites. In contrast, the controlled mesoporosity andstrong acidity of fully crystalline mesostructured zeolites provideaccessibility to the acidic sites and acidity that allows for the deeperHDS required for meeting future environmental restrictions.

In other various embodiments, mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructuredmaterials can be used in hydrocracking Metals, including noble metalssuch as, for example, Ni, Co, W, and Mo, and metal compounds arecommercially used in hydrocracking reactions. These metals can besupported on mesostructured materials by previously described methods.The mesostructured materials including metals can be employed forhydrocracking of various feedstocks such as, for example, petrochemicaland hydrocarbon feed materials.

Typically, hydrocracking involves passing a feed stock (i.e., a feedmaterial), such as the heavy fraction, through one or more hydrocrackingcatalyst beds under conditions of elevated temperature and/or pressure.The plurality of catalyst beds may function to remove impurities such asany metals and other solids. The catalyst beads also crack or convertthe longer chain molecules in the feedstock into smaller ones.Hydrocracking can be effected by contacting the particular fraction orcombination of fractions with hydrogen in the presence of a suitablecatalyst at conditions, including temperatures in the range of fromabout 600 to about 900° F. and at pressures from about 200 to about4,000 psia, using space velocities based on the hydrocarbon feedstock ofabout 0.1 to 10 hr⁻¹.

As compared to conventional unmodified catalyst supports such as, forexample, alumina, silica, and zeolites, the mesostructured materialsincluding metals allow for the hydrocracking of higher boiling pointfeed materials. The mesostructured materials including metals produce alow concentration of heteroatoms and a low concentration of aromaticcompounds. The mesostructured materials including metals exhibitbifunctional activity. The metal, for example a noble metal, catalyzesthe dissociative adsorption of hydrogen and the mesostructured materialprovides the acidity.

The controlled pore size and controlled mesopore surface in themesostructured materials including metals can make the bifunctionalactivity more efficiently present in the mesostructured catalysts ascompared to a bifunctional conventional catalyst. In addition to thezeolitic acidity present in the fully crystalline mesostructuredzeolites, the controlled pore size enables larger pores that allow for ahigh dispersion of the metal phase and the processing of largehydrocarbons.

In other embodiments, mesostructured materials (e.g., fully crystallinemesostructured zeolites) and/or crystalline nanostructured materials canbe used in hydroisomerization. Various metals and mixtures of metals,including, for example, noble metals such as nickel or molybdenum andcombinations thereof in, for example, their acidic form, can besupported on mesostructured materials.

Typically, hydroisomerization is used to convert linear paraffins tobranched paraffins in the presence of a catalyst and in a hydrogen-richatmosphere. Hydroisomerization catalysts useful for isomerizationprocesses are generally bifunctional catalysts that include adehydrogenation/hydrogenation component and an acidic component.Paraffins were exposed to fully crystalline mesostructured zeolitesincluding metals and were isomerized in a hydrogen flow at a temperatureranging from about 150 to about 350° C. thereby producing branchedhydrocarbons and high octane products. The fully crystallinemesostructured zeolites including metals permit hydroisomerization ofbulkier molecules than is possible with commercial conventionalcatalysts due, at least in part, to their controlled pore size and porevolume.

In other embodiments, mesostructured materials (e.g., fully crystallinemesostructured zeolites) and/or crystalline nanostructured materials canbe used in the oligomerization of olefins. The controlled pore shape,pore size, and pore volume improves the selectivity properties of themesostructured materials. The selectivity properties, the increasedsurface area present in the mesospore surfaces, and the more openstructure of the mesostructured materials can be used to control thecontact time of the reactants, reactions, and products inside themesostructured materials. The olefin can contact the mesostructuredmaterials at relatively low temperatures to produce mainlymiddle-distillate products via olefin-oligomerization reactions. Byincreasing the reaction temperature, gasoline can be produced as theprimary fraction.

Where the mesostructured materials are used in FCC processes, the yieldof olefins production can be increased relative to FCC with conventionalzeolites. The increased yield of olefins can be reacted byoligomerization in an olefin-to-gasoline- and/or -diesel process, suchas, for example, MOGD (Mobile Olefins to Gas and Diesel, a process toconvert olefins to gas and diesel). In addition, olefins of more complexstructure can be oligomerized using the mesostructured materialsdescribed herein.

The LPG fraction produced using mesostructured materials has a higherconcentration of olefins compared to other catalysts, including, forexample, various conventional FCC catalysts, zeolites, metals oxides,and clays under catalytic cracking conditions both in fixed bed andfluidized bed reactor conditions. The mesopore size of themesostructured materials readily allows the cracked products to exit themesostructured materials. Accordingly, hydrogen transfer reactions arereduced and the undesired transformation of olefins to paraffins in theLPG fraction is reduced. In addition, over-cracking and coke formationare limited, which increases the average life time of the catalyst.

The controlled pore size, pore volume, and mesopore surfaces provide anopen structure in the mesotructured materials. This open structurereduces the hydrogen transfer reactions in the gasoline fraction andlimits the undesired transformation of olefins and naphthenes intoparaffins and aromatics. As a result, the octane number (both RON andMON) of the gasoline produced using the mesostructured materials isincreased.

The acidity and the controlled mesoporosity present in themesostructured materials can enable their use in alkylation reactions.Specifically, olefins and paraffins react in the presence of themesostructured materials to produce highly branched octanes. The highlybranched octane products readily exit the open structure of the fullycrystalline mesostructured materials, thereby minimizing unwanted olefinoligomerization.

In other embodiments, the mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructuredmaterials can be used to process a petrochemical feed material topetrochemical product by employing any of a number of shape selectivepetrochemical and/or hydrocarbon conversion processes. In oneembodiment, a petrochemical feed can be contacted with themesostructured material under reaction conditions suitable fordehydrogenating hydrocarbon compounds. Generally, such reactionconditions include, for example, a temperature of from about 300 toabout 700° C., a pressure from about 0.1 to about 10 atm, and a WHSVfrom about 0.1 to about 20 hr⁻¹.

In other embodiments, a petrochemical feed can be contacted with themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials under reactionconditions suitable for converting paraffins to aromatics. Generally,such reaction conditions include, for example, a temperature of fromabout 300 to about 700° C., a pressure from about 0.1 to about 60 atm, aWHSV of from about 0.5 to about 400 hr⁻¹, and an H₂/HC mole ratio offrom about 0 to about 20.

In other embodiments, a petrochemical feed can be contacted with themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials under reactionconditions suitable for converting olefins to aromatics. Generally, suchreaction conditions include, for example, a temperature of from about100 to about 700° C., a pressure from about 0.1 to about 60 atm, a WHSVof from about 0.5 to about 400 hr⁻¹, and an H₂/HC mole ratio from about0 to about 20.

In other embodiments, a petrochemical feed can be contacted with themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials under reactionconditions suitable for isomerizing alkyl aromatic feedstock components.Generally, such reaction conditions include, for example, a temperatureof from about 230 to about 510° C., a pressure from about 3 to about 35atm, a WHSV of from about 0.1 to about 200 hr⁻¹, and an H₂/HC mole ratioof from about 0 to about 100.

In other embodiments, a petrochemical feed can be contacted with themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials under reactionsconditions suitable for disproportionating alkyl aromatic components.Generally, such reaction conditions include, for example, a temperatureranging from about 200 to about 760° C., a pressure ranging from about 1to about 60 atm, and a WHSV of from about 0.08 to about 20 hr⁻¹.

In other embodiments, a petrochemical feed can be contacted with themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials under reactionconditions suitable for alkylating aromatic hydrocarbons (e.g., benzeneand alkylbenzenes) in the presence of an alkylating agent (e.g.,olefins, formaldehyde, alkyl halides and alcohols). Generally, suchreaction conditions include a temperature of from about 250 to about500° C., a pressure from about 1 to about 200 atm, a WHSV of from about2 to about 2,000 hr⁻¹, and an aromatic hydrocarbon/alkylating agent moleratio of from about 1/1 to about 20/1.

In other embodiments, a petrochemical feed can be contacted with themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials under reactionconditions suitable for transalkylating aromatic hydrocarbons in thepresence of polyalkylaromatic hydrocarbons. Generally, such reactionconditions include, for example, a temperature of from about 340 toabout 500° C., a pressure from about 1 to about 200 atm, a WHSV of fromabout 10 to about 1,000 hr⁻¹, and an aromatichydrocarbon/polyalkylaromatic hydrocarbon mole ratio of from about 1/1to about 16/1.

Generally, suitable conditions for a petrochemical or hydrocarbon feedto contact the mesostructured materials (e.g., fully crystallinemesostructured zeolites) and/or crystalline nanostructured materialsinclude temperatures ranging from about 100 to about 760° C., pressuresranging from above 0 to about 3,000 psig, a WHSV of from about 0.08 toabout 2,000 hr⁻¹, and a hydrocarbon compound mole ratio of from 0 toabout 100.

Application in Compound Removal

The microporosity, mesoporosity, and ion exchange properties present inthe mesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or in crystalline nanostructured materials can enableremoval of inorganic and organic compounds from solutions. Suitablesolutions can be aqueous or organic solutions. Accordingly, themesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials can be employed inwater treatment, water purification, pollutant removal, and/or solventdrying.

For example, 1 gram of N⁺ and a fully crystalline mesostructured zeoliteis suspended in 1 L of a methylene blue aqueous solution, stirred for 12hours, and filtered. The fully crystalline mesostructured zeoliteremoves the methylene blue from the aqueous solution. Otherconfigurations such as fixed bed, filters, and membranes can be alsoused in addition to the mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or crystalline nanostructuredmaterials. Optionally, fully crystalline mesostructured zeolites and/orcrystalline nanostructured zeolites can be employed as additives withconventional separation means, for example, fixed bed, filters, andmembranes. The fully crystalline mesostructured zeolites and/orcrystalline nanostructured zeolites can be substituted for otherseparation means in, for example, fixed bed, filters, and membranes. Thefully crystalline mesostructured zeolites and/or crystallinenanostructured zeolites can be recycled by ion exchange, drying,calcinations or other conventional techniques and reused.

Application in Adsorption

The mesostructured materials (e.g., fully crystalline mesostructuredzeolites) and/or crystalline nanostructured materials can be used toadsorb gaseous compounds including, for example, volatile organiccompounds (“VOCs”), which are too bulky to be adsorbed by conventionalunmodified zeolites. Accordingly, pollutants that are too bulky to beremoved by conventional unmodified zeolites can be removed from agaseous phase by direct adsorption. When the mesostructured ornanostructured material is a zeolite, the fully crystallinemesostructured zeolites and/or crystalline nanostructured zeolites canbe employed for adsorption in various adsorption configurations such as,for example, membranes, filters and fixed beds. Adsorbed organiccompounds can be desorbed from the fully crystalline mesostructuredzeolites and/or crystalline nanostructured zeolites by heat treatment.Thus, the fully crystalline mesostructured zeolites and/or crystallinenanostructured zeolites can be recycled and then reused.

Application in Gas Separation

Fully crystalline mesostructured zeolites and/or crystallinenanostructured zeolites can be grown on various supports by employedtechniques such as, for example, seeding, hydrothermal treatment, dipcoating, and/or use of organic compounds. They can be physically mixedwith conventional zeolites or metal oxides. Continuous layers of fullycrystalline mesostructured zeolites and/or crystalline nanostructuredzeolites can be used as membranes and/or catalytic membranes on, forexample, porous supports.

Fully crystalline mesostructured zeolites and/or crystallinenanostructured zeolites are unique molecular sieves containing bothmicroporosity and mesoporosity. They may be employed in variousconfigurations including, for example, membranes for separation of gasesbased on physicochemical properties such as, for example, size, shape,chemical affinity, and physical properties.

Application in Fine Chemicals and Pharmaceuticals

A fully crystalline mesostructured zeolite has increased active siteaccessibility as compared to the same zeolite in conventional form.Similarly, crystalline nanostructure zeolites have increased active siteaccessibility compared to the same zeolite in conventional form.Accordingly, the activity of some important chemical reactions used infine chemical and pharmaceutical production can be improved bysubstituting a conventional zeolite used in the process for a fullycrystalline mesostructured zeolite and/or a crystalline nanostructurezeolite. In addition, a fully crystalline mesostructured zeolite and/ora crystalline nanostructure zeolite may be employed as an additive to acatalyst typically employed in such fine chemical and pharmaceuticalproduction reactions. Suitable processes that can be improved by using afully crystalline mesostructured zeolite and/or a crystallinenanostructure zeolite include, for example, isomerization of olefins,isomerization of functionalized saturated systems, ring enlargementreactions, Beckman rearrangements, isomerization of arenes, alkylationof aromatic compounds, acylation of arenes, ethers, and aromatics,nitration and halogenation of aromatics, hydroxyalylation of arenes,carbocyclic ring formation (including Diels-Alder cycloadditions), ringclosure towards heterocyclic compounds, amination reactions (includingamination of alcohols and olefins), nucleophilic addition to epoxides,addition to oxygen-compounds to olefins, esterification, acetalization,addition of heteroatom compounds to olefins, oxidation/reductionreactions such as, but not limited to, Meerwein-Ponndorf-Verleyreduction and Oppenauer oxidation, dehydration reactions, condensationreactions, C—C formation reactions, hydroformylation, acetilization, andamidation.

Application in Slow Release Systems

Chemicals and/or materials having useful properties such as, forexample, drugs, pharmaceuticals, fine chemicals, optic, conducting,semiconducting magnetic materials, nanoparticles, or combinationsthereof, can be introduced to mesostructured materials (e.g., fullycrystalline mesostructured zeolites) and/or a crystalline nanostructuredmaterials using one or more of the modifying methods described herein.For example, chemicals and/or materials may be incorporated into themesostructured materials by, for example, adsorption or ion exchange. Inaddition, such useful chemicals can be combined with the mesostructuredmaterials and/or crystalline nanostructure materials by creating aphysical mixture, a chemical reaction, heat treatment, irradiation,ultrasonication, or any combination thereof.

The release of the chemicals and/or materials having useful propertiescan be controlled. Controlled release may take place in various systemssuch as, for example, chemical reactions, living organisms, blood, soil,water, and air. The controlled release can be accomplished by physicalreactions or by chemical reactions. For example, controlled release canbe accomplished by chemical reactions, pH variation, concentrationgradients, osmosis, heat treatment, irradiation, and/or magnetic fields.

Kits

One or more embodiments also provide kits for conveniently andeffectively implementing various methods described herein. Such kits cancomprise any of the mesostructured and/or nanostructured materials(e.g., zeolitic structures) described herein, and a means forfacilitating their use consistent with various methods. Such kits mayprovide a convenient and effective means for assuring that the methodsare practiced in an effective manner. The compliance means of such kitsmay include any means that facilitate practicing one or more methodsassociated with the materials described herein. Such compliance meansmay include instructions, packaging, dispensing means, or combinationsthereof. Kit components may be packaged for either manual or partiallyor wholly automated practice of the foregoing methods. In otherembodiments involving kits, a kit is contemplated that includes blockcopolymers, and optionally instructions for their use.

EXAMPLE

An example of a shaped zeolitic material was made as follows. Initially,a 30% solids slurry in water was made containing an insoluble portioncomprising 62% by weight kaolin clay that had been calcined through itsexotherm at about 1,780° F. without substantial formation of mullite(SATINTONE® SHB, available from BASF) and 38% by weight hydrous kaolinclay (ASP-200, available from BASF); and a soluble portion consisting ofsodium silicate solution (N®, available from PQ Corp.) in an amountwhere the silica in the sodium silicate was 8% of the combined weight ofSatintone and ASP clays in the slurry. The resulting slurry was spraydried into microspheres having nominal diameters of between about 40 and100 microns using a Stork-Bowen model BE-1240 spray dryer with an inlettemperature of about 400° C. and an outlet temperature of about 120° C.The resultant microspheres were calcined for between 2 and 4 hours at atemperature of between about 1,100 and 1,300° F. to dehydrate thehydrous kaolin constituent and convert it to the metakaolin phase.

Calcined microspheres were converted into zeolite-containing shapedarticles by crystallization of sodium Y faujasite zeolite within themicrospheres, as follows. Crystallization initiator (seeds) was preparedby adding, in order with mild stirring to a PYREX® glass beaker: 214.5 gof deionized water, 64.4 g of 50% sodium hydroxide solution, and 38.8 gof sodium aluminate solution containing 23.5% Al₂O₂ and 19.4% Na₂O. Tothat was added rapidly and with vigorous stirring, 256.0 g of sodiumsilicate solution (D™, available from PQ Corp.). The mixture was allowedto age for 20 hours at 37° C. The reaction was then quenched by addingsodium silicate solution comprising 194.6 g of D™ sodium silicatesolution and 31.7 g of deionized water, and cooling to ambienttemperature. To that mixture was added 800 g of N® sodium silicatesolution. In a 1 liter PYREX® resin kettle, 229.2 g of quenched seedswere combined with 257.0 g of N® sodium silicate solution, 85.2 g of 50%sodium hydroxide solution, and 254.8 g of water. With mixing, to thatwas added 250 g of calcined microspheres, as prepared above, containingSATINTONE® 5HB calcined kaolin and metakaolin. With continued slowstirring to suspend the solids, the mixture was heated to about 210° F.and maintained at that temperature for 24 hours. After 24 hours, thematerial was filtered over Whatman 42 paper, washed with deionizedwater, and dried at 80° C. to produce zeolitic microspheres.

Samples of the zeolitic microspheres were analyzed by X-ray diffractionfor crystallinity, zeolite unit cell size (an indirect measure of theSiO₂/Al₂O₃ ratio of the zeolite) and by argon adsorption to determinetheir pore size distribution. The results of the X-ray diffractionanalysis are shown in Table 1 below. For comparison, results are alsoshown for CBV-100 zeolite, a high purity sodium Y faujasite produced byZeolyst. The results show that the zeolitic microspheres contained about64% by weight Y faujasite zeolite with a unit cell size and silica toalumina ratio equivalent to that of CBV-100.

Also included for comparison is FIG. 24, which presents the full X-raydiffraction scans for the two materials showing sharp, well definedpeaks characteristic of well crystallized Y faujasite zeolite.

TABLE 1 X-Ray Diffraction of Zeolitic Microspheres Material Unit CellSize SiO₂/Al₂O₃ Ratio Crystallinity Zeolitic Microspheres 24.673(1) 5.1764 CBV-100 24.683(2) 5.06 100

A portion of the zeolitic microspheres were processed as follows toimpart mesoporosity into the shaped articles. 4.17 g of zeoliticmicrospheres were added to 15.0 mL of water (solution A). Then asolution (B) containing 0.96 g of citric acid dissolved in 5.76 mL ofwater was added dropwise, with stirring to solution A over 10 minutes.The resultant mixture (A+B) was stirred for an additional 1 hour at roomtemperature. The solid was separated from the mixture by filtration,washed with deionized water, and dried to produce acid-treatedmicrospheres.

Additional mesoporosity was formed within the acid-treated microspheresas follows. 1.67 g of acid-treated microspheres was added to a solution(C) containing 0.50 g of cetyltrimethylammonium bromide (“CTAB”)dissolved in 6.25 mL of water. Then 0.90 mL of concentrated (30%)ammonium hydroxide solution was added. The mixture was stirred for 10minutes and then maintained overnight without stirring in a sealedvessel at 80° C. for 24 hours. The resultant solid was filtered, washedwith deionized water, and dried. CTA entrained within the treatedmicrospheres was removed by heat treatment, first in N₂ at 550° C. for 4hours (degradation/carbonization) and then in synthetic air at 550° C.for 8 hours (burning).

The pore size distributions of the zeolitic microspheres bothas-synthesized and after treatment to impart mesoporosity are shown inFIG. 25. The graph of FIG. 25 shows that the as-synthesized microspheresalready contained a significant amount of mesoporosity at about 60angstroms diameter. This is believed to be the result of alkalineextraction of silica from the kaolin clay that had been calcined throughits exotherm, leaving an alumina-rich alkaline extraction residue ofcalcined clay. The metakaolin constituent of the precursor microspheresis believed to have been substantially consumed and converted to zeoliteduring the crystallization reaction. The volume of mesopores in theas-synthesized material was about 0.09 cc/g.

After treatment to impart additional mesoporosity, there were 2 distinctchanges in the pore structure of the material. First, the material nolonger exhibited mesopores in the range around 60 Å diameter. Instead,it showed mesopores at around 40 Å diameter, and the volume of mesoporeswas nearly doubled to about 0.17 cc/g.

The X-ray diffraction pattern of the zeolitic microspheres withadditional mesoporosity (mesoporous in situ FCC) is shown in FIG. 26,along with the diffraction patterns of untreated zeolitic microspheres(in situ FCC) and a reference ultrastabilized Y zeolite (“USY”). Thegraph of FIG. 26 shows that, except for a slight reduction in peakintensity consistent with the lower microporosity of the mesoporousmicrospheres relative to the untreated zeolitic microspheres, thepatterns are the same. This indicates that there were no othercrystalline phases produced during the processing to impart additionalmesoporosity to the zeolitic microspheres. Also, there is no “amorphoushump” in the range of about 10 to 25 degrees 2 theta for the mesoporousmicrospheres, indicating that there was no substantial formation ofnon-crystalline material due to the processing to impart additionalmesoporosity.

Shown in FIGS. 27a-e are a series of scanning electron photomicrographsat increasing magnification showing the zeolitic microspheres havingadditional mesoporosity. They illustrate the generally spherical shapeof the microspheres that is substantially retained after processing toimpart additional mesoporosity, and that the microspheres are comprisedof a multiplicity of separate particles aggregated into porous shapes.Individual zeolite crystals may be seen most clearly in thephotomicrograph at 20,000× (FIG. 27e ). They are the angular structureswith an average size of about 0.1-0.4 micrometers (μm).

FIG. 28 displays transmission electron photomicrographs of an individualzeolite crystal within a zeolitic microsphere having additionalmesoporosity (in situ FCC catalyst). They show areas with the regulargrid structure of micropores that is characteristic of crystallinezeolite Y faujasite, and also show regions having a combination of theregular grid structure and larger, less ordered pores of a larger size(mesopores). This illustrates that at least a portion of the additionalmesoporosity was located within crystalline zeolite (i.e., zeoliteintracrystalline mesoporosity).

SELECTED DEFINITIONS

It should be understood that the following is not intended to be anexclusive list of defined terms. Other definitions may be provided inthe foregoing description, such as, for example, when accompanying theuse of a defined term in context.

As used herein, the terms “a,” “an,” and “the” mean one or more.

As used herein, the term “and/or,” when used in a list of two or moreitems, means that any one of the listed items can be employed by itselfor any combination of two or more of the listed items can be employed.For example, if a composition is described as containing components A,B, and/or C, the composition can contain A alone; B alone; C alone; Aand B in combination; A and C in combination, B and C in combination; orA, B, and C in combination.

The term “catalyst” is art-recognized and refers to any substance thatnotably affects the rate of a chemical reaction without itself beingconsumed or significantly altered.

The term “cracking” is art-recognized and refers to any process ofbreaking up organic compounds into smaller molecules.

As used herein, the terms “comprising,” “comprises,” and “comprise” areopen-ended transition terms used to transition from a subject recitedbefore the term to one or more elements recited after the term, wherethe element or elements listed after the transition term are notnecessarily the only elements that make up the subject.

As used herein, the terms “having,” “has,” and “have” have the sameopen-ended meaning as “comprising,” “comprises,” and “comprise” providedabove.

As used herein, the terms “including,” “includes,” and “include” havethe same open-ended meaning as “comprising,” “comprises,” and “comprise”provided above.

The term “including” is used to mean “including but not limited to.”“Including” and “including but not limited to” are used interchangeably.

“MCM-41” refers to a Mobil composite of matter that is an amorphousmesoporous silica with a hexagonal pore arrangement, where the mean porediameter is in the range of about 2 to 10 nm.

“MCM-48” refers to a Mobil composite of matter that is an amorphousmesoporous silica with a cubic pore arrangement, where the mean porediameter is in the range of about 2 to 10 nm.

“MCM-50” refers to a Mobil composite of matter that is an amorphousmesoporous silica with a lamellar pore arrangement, where the mean porediameter is in the range of about 2 to 10 nm.

The term “mesoporous” is art-recognized and refers to a porous materialcomprising pores with an intermediate size, ranging anywhere from about2 to about 60 nanometers (20 to 600 angstroms).

The term “mesostructure” is art-recognized and refers to a structurecomprising mesopores which control the architecture of the material atthe mesoscopic or nanometer scale, including ordered and non-orderedmesostructured materials, as well as nanostructured materials (i.e.,materials in which at least one of their dimension is in the nanometersize range) such as nanotubes, nanorings, nanorods, nanowires,nanoslabs, and the like.

The term “mesostructured zeolites” as used herein includes allcrystalline mesoporous materials, such as zeolites, aluminophosphates,gallophosphates, zincophosphates, titanophosphates, etc. Amesostructured zeolite may be in the form of ordered mesporosity (as in,for example MCM-41, MCM-48 or SBA-15), non-ordered mesoporosity (as inmesocellular foams (“MCF”)), or mesoscale morphology (as in nanorods andnanotubes). The notation zeolite [mesostructure] is used to designatethe different types of mesostructured zeolites.

“MOR” refers to mordenite, which is a zeolite comprising approximately 2moles of sodium and potassium and approximately 1 mole of calcium in itsorthorhombic crystal structure. This term also includes the acidic formof MOR which may also be represented as “H-MOR.”

“MSU-S (MFI)” represents a mesoporous material made with nanosizedzeolites with a pore range of about 2-15 nm. The (MFI) refers to itsstructure.

“MSU-S (BEA)” represents a mesoporous material made with nanosizedzeolites with a pore range of about 1-15 nm. The (BEA) refers to itsstructure.

“PNA” represents a semicrystallized form of MCM-41.

“SBA-15” represents mesoporous (alumino) silicas with pore diameters upto 30 nm arranged in a hexagonal manner and pore walls up to 6 nm thick.

The term “surfactant” is art-recognized and refers to any surface-activeagent or substance that modifies the nature of surfaces, often reducingthe surface tension of water. Cetyltrimethylammonium bromide is anon-limiting example of a surfactant.

“Y” represents a faujasite which is a zeolite comprising 2 moles ofsodium and 1 mole of calcium in its octahedral crystal structure. Thisterm also includes the acidic form of Y which may also be represented as“H—Y.”

The term “zeolite” is defined as in the International ZeoliteAssociation Constitution (Section 1.3) to include both natural andsynthetic zeolites as well as molecular sieves and other microporous andmesoporous materials having related properties and/or structures. Theterm “zeolite” also refers to a group, or any member of a group, ofstructured aluminosilicate minerals comprising cations such as sodiumand calcium or, less commonly, barium, beryllium, lithium, potassium,magnesium and strontium; characterized by the ratio(Al+Si):O=approximately 1:2, an open tetrahedral framework structurecapable of ion exchange, and loosely held water molecules that allowreversible dehydration. The term “zeolite” also includes“zeolite-related materials” or “zeotypes” which are prepared byreplacing Si⁴⁺ or Al³⁺ with other elements as in the case ofaluminophosphates (e.g., MeAPO, SAPO, E1APO, MeAPSO, and E1APSO),gallophosphates, zincophophates, titanosilicates, etc.

“ZSM-5” or “ZSM-5 (MFI)” represents a Mobil synthetic zeolite-5. Thisterm also includes the acidic form of ZSM-5 which may also berepresented as “H-ZSM-5.” The (MFI) relates to its structure.

A comprehensive list of the abbreviations utilized by organic chemistsof ordinary skill in the art appears in the first issue of each volumeof the Journal of Organic Chemistry; this list is typically presented ina table entitled Standard List of Abbreviations.

Contemplated equivalents of the zeolitic structures, subunits and othercompositions described above include such materials which otherwisecorrespond thereto, and which have the same general properties thereof(e.g., biocompatible), wherein one or more simple variations ofsubstituents are made which do not adversely affect the efficacy of suchmolecule to achieve its intended purpose.

Numerical Ranges

The present description uses numerical ranges to quantify certainparameters relating to the invention. It should be understood that whennumerical ranges are provided, such ranges are to be construed asproviding literal support for claim limitations that only recite thelower value of the range as well as claim limitations that only recitethe upper value of the range. For example, a disclosed numerical rangeof 10 to 100 provides literal support for a claim reciting “greater than10” (with no upper bounds) and a claim reciting “less than 100” (with nolower bounds).

The present description uses specific numerical values to quantifycertain parameters relating to the invention, where the specificnumerical values are not expressly part of a numerical range. It shouldbe understood that each specific numerical value provided herein is tobe construed as providing literal support for a broad, intermediate, andnarrow range. The broad range associated with each specific numericalvalue is the numerical value plus and minus 60 percent of the numericalvalue, rounded to two significant digits. The intermediate rangeassociated with each specific numerical value is the numerical valueplus and minus 30 percent of the numerical value, rounded to twosignificant digits. The narrow range associated with each specificnumerical value is the numerical value plus and minus 15 percent of thenumerical value, rounded to two significant digits. For example, if thespecification describes a specific temperature of 62° F., such adescription provides literal support for a broad numerical range of 25°F. to 99° F. (62° F.+/−37° F.), an intermediate numerical range of 43°F. to 81° F. (62° F.+/−19° F.), and a narrow numerical range of 53° F.to 71° F. (62° F.+/−9° F.). These broad, intermediate, and narrownumerical ranges should be applied not only to the specific values, butshould also be applied to differences between these specific values.Thus, if the specification describes a first pressure of 110 psia and asecond pressure of 48 psia (a difference of 62 psi), the broad,intermediate, and narrow ranges for the pressure difference betweenthese two streams would be 25 to 99 psi, 43 to 81 psi, and 53 to 71 psi,respectively.

CLAIMS NOT LIMITED TO DISCLOSED EMBODIMENTS

The preferred forms of the invention described above are to be used asillustration only, and should not be used in a limiting sense tointerpret the scope of the present invention. Modifications to theexemplary embodiments, set forth above, could be readily made by thoseskilled in the art without departing from the spirit of the presentinvention.

The inventors hereby state their intent to rely on the Doctrine ofEquivalents to determine and assess the reasonably fair scope of thepresent invention as it pertains to any apparatus not materiallydeparting from but outside the literal scope of the invention as setforth in the following claims.

What is claimed is:
 1. A method of preparing a shaped zeolitic materialwith enhanced mesoporosity, said method comprising: (a) synthesizing acomposite shaped article comprising at least one zeolite and at leastone non-zeolitic material, wherein said zeolite comprises analuminosilicate zeolite having a SiO₂/Al₂O₃ ratio below about 20; and(b) contacting said composite shaped article with at least one pHcontrolling agent and at least one surfactant under conditionssufficient to increase the pore volume of at least one 10 angstromsubset of mesoporosity in said composite shaped article, thereby formingsaid shaped zeolitic material with enhanced mesoporosity, wherein saidpH controlling agent comprises an acid or a base, wherein saidcontacting of step (b) causes a net mesopore increase in said zeolite ofsaid composite shaped article.
 2. The method of claim 1, wherein saidcontacting of step (b) causes a net increase of at least 10 percent inthe overall mesoporosity of said composite shaped article, wherein saidshaped zeolitic material has a total volume of mesopores in the range offrom about 0.05 to about 0.9 cc/g.
 3. The method of claim 1, whereinsaid increase in pore volume of said 10 angstrom subset constitutes anincrease of at least 0.01 cc/g in said 10 angstrom subset.
 4. The methodof claim 1, wherein said increase in pore volume of said 10 angstromsubset constitutes an increase of at least 10 percent of the pore volumeof said 10 angstrom subset.
 5. The method of claim 1, wherein said 10angstrom subset is contained within a range of 20 to 250 angstroms. 6.The method of claim 1, wherein step (a) includes the substeps of: (i)combining said at least one non-zeolitic material and said at least onezeolite to thereby form an initial mixture; and (ii) shaping saidinitial mixture into said composite shaped article.
 7. The method ofclaim 1, wherein said at least one non-zeolitic material comprisesaluminum oxide, titanium dioxide, zirconium oxide, mullite, hydrouskaolin clay, the residue of alkaline extraction of kaolin clay that hasbeen calcined through the characteristic exotherm at about 1,780° F.without substantial formation of mullite, silicon carbide, siliconnitride, or mixtures thereof.
 8. The method of claim 1, furthercomprising treating at least a portion of said shaped zeolitic materialto extract at least a portion of aluminum therefrom.
 9. The method ofclaim 1, wherein said zeolite comprises faujasite.
 10. The method ofclaim 1, wherein said surfactant comprises a cationic surfactant. 11.The method of claim 1, wherein said surfactant comprises analkylammonium halide.
 12. The method of claim 1, wherein the reactiontemperature of step (b) is in the range of from about 60 to about 100°C.
 13. The method of claim 1, wherein said composite shaped articlecomprises said zeolite in an amount in the range of from about 0.1 toabout 99 weight percent.
 14. The method of claim 1, wherein said pHcontrolling agent comprises a base.
 15. A method of preparing a shapedzeolitic material with enhanced mesoporosity, said method comprising:(a) synthesizing a composite shaped article comprising at least onezeolite and at least one non-zeolitic material, wherein said zeolitecomprises faujasite, mordenite, ZSM-5, CHA, or mixtures thereof; and (b)contacting said composite shaped article with an acid to form anacid-treated shaped article, wherein said contacting further comprisescontacting said composite shaped article with at least one surfactantprior to, during, or after said contacting with said acid; and (c)contacting said acid-treated shaped article with a base to form abase-treated shaped article, wherein said base-treated shaped articlehas an overall mesoporosity that is at least 0.05 cc/g greater than saidcomposite shaped article.
 16. The method of claim 15, wherein saidbase-treated shaped article has an overall mesoporosity that is at least0.1 cc/g greater than said composite shaped article, wherein saidbase-treated shaped article has a total volume of mesopores in the rangeof from about 0.05 to about 0.9 cc/g.
 17. The method of claim 15,wherein said base-treated shaped article has an overall mesoporositythat is at least 50 percent greater than the overall mesoporosity ofsaid composite shaped article.
 18. The method of claim 15, wherein saidbase-treated shaped article comprises a mesostructured zeolite.
 19. Themethod of claim 15, wherein said surfactant comprises an alkylammoniumhalide.
 20. A method of preparing a shaped zeolitic material withenhanced mesoporosity, said method comprising: (a) synthesizing acomposite shaped article comprising at least one zeolite and at leastone non-zeolitic material, wherein said zeolite comprises analuminosilicate zeolite having a SiO₂/Al₂O₃ ratio below about 20; (b)contacting said composite shaped article with an acid to form anacid-treated shaped article; (c) contacting said composite shapedarticle with at least one surfactant prior to, during, or after saidcontacting with said acid; and (d) contacting said acid-treated shapedarticle with a base to form a base-treated shaped article, wherein saidbase-treated shaped article has an overall mesoporosity that is greaterthan said composite shaped article.
 21. The method of claim 20, whereinsaid base-treated shaped article has an overall mesoporosity that is atleast 0.05 cc/g greater than said composite shaped article, wherein saidbase-treated shaped article has a total volume of mesopores in the rangeof from about 0.05 to about 0.9 cc/g.
 22. The method of claim 20,wherein said base-treated shaped article has an overall mesoporositythat is at least 50 percent greater than the overall mesoporosity ofsaid composite shaped article.
 23. The method of claim 20, wherein saidbase-treated shaped article comprises a mesostructured zeolite.
 24. Themethod of claim 20, wherein said surfactant comprises a cationicsurfactant.
 25. The method of claim 20, wherein said zeolite comprisesfaujasite, mordenite, ZSM-5, CHA, or mixtures thereof.
 26. The method ofclaim 20, wherein said at least one non-zeolitic material comprisesaluminum oxide, titanium dioxide, zirconium oxide, mullite, hydrouskaolin clay, the residue of alkaline extraction of kaolin clay that hasbeen calcined through the characteristic exotherm at about 1,780° F.without substantial formation of mullite, silicon carbide, siliconnitride, or mixtures thereof.
 27. The method of claim 20, wherein saidcomposite shaped article comprises said zeolite in an amount in therange of from about 0.1 to about 99 weight percent.